Nanoscale characterization of surfaces and interfaces

N. John DiNardo Nanoscale Characterization of Surfaces and Interfaces Weinheim - New York Base1 - Cambridge Tokyo T...

Author: N. John DiNardo

151 downloads 1130 Views 14MB Size Report

This content was uploaded by our users and we assume good faith they have the permission to share this book. If you own the copyright to this book and it is wrongfully on our website, we offer a simple DMCA procedure to remove your content from our site. Start by pressing the button below!
Report copyright / DMCA form

DOWNLOAD PDF

N. John DiNardo

Nanoscale Characterization of Surfaces and Interfaces

Weinheim - New York Base1 - Cambridge Tokyo

This Page Intentionally Left Blank

N. John DiNardo


VCH

0 VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1994

Distribution: VCH, P.O.Box 101161, D-69451 Weinheim, Federal Republic of Germany Switzerland: VCH, P.O.Box, CH-4020 Basel, Switzerland United Kingdom and Ireland: VCH, 8 Wellington Court, Cambridge CB1 MZ, United Kingdom USA and Canada: VCH, 220 East 23rd Street, New York,NY 10010-4606, USA Japan: VCH, Eikow Building, 10-9 Hongo 1-chome, Bunkyo-ku, Tokyo 113, Japan ISBN 3-527-29247-0

N. John DiNardo


Weinheim - New York Base1 - Cambridge Tokyo

N. John DiNardo Department of Physics and Atmospheric Science Drexel University Philadelphia, PA 19104 USA This book was carefully produced. Nevertheless, author, editors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Published jointly by VCH Verlagsgesellschaft,Weinheim (Federal Republic of Germany) VCH Publishers, New York, NY (USA)

Editorial Directors: Dr. Peter Gregory, Deborah Hollis, Dr. Ute Anton Production Manager: Dipl. Wirt.-Ing. (FH) Hans-Jochen Schmitt

Cover Illustration: Adapted from an AFM image of a thermally-treated diamond-like-carbon film (see Preface)

Library of Congress Card No. applied for

A catalogue record for this book is available from the British Library

Die Deutsche Bibliothek - CIP-Einheitsaufnahme DiNardo, N. John: Nanoscale characterization of surfaces and interfaces / N. John DiNardo. - Weinheim ; New York ;Base1 ; Cambridge ;Tokyo : VCH, 1994 ISBN 3-527-29247-0

0 VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1994

Printed on acid-free and low chlorine paper All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means - nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition, Printing and Bookbinding: Konrad Triltsch, Druck- und Verlagsanstalt GmbH, D-97070 Wiirzburg Printed in the Federal Republic of Germany

To my wife, Trudy, and our children, Christopher and Johanna

STM image of the Si(ll1) surface acquired with a JEOL JSTM-4500VT microscope. This image shows reconstructed 7 X 7 regions terminated by surface steps which surround a terrace on which a Ag/Si( 111)-3x 1 reconstructed region has formed. Position-dependent tunneling spectra find that, electronically, the 7 X 7 regions appear metallic while the 3 X 1region exhibits a 1.1eV energy gap. (J. Carpinelliand H. H . Weitering, University of TennesseelOak Ridge National Laboratory)

An AFM image of a thermally-treated 500 A-thick diamond-like-carbon film grown on a Pt substrate by laser ablation using a Digital Instruments Nanoscope 111. Thermal processing alters the morphology of the initially flat film by apparently relieving internal stresses, resulting in partial separation of the film from the substrate. (T. W Mercer, N . J . DiNardo, Drexel University and Laboratory for Research on the Structure of Matter, University of Pennsylvania; M . I? Siegel, Sandia National Laboratory)

Preface

The invention of the STM by G . Binnig and H. Rohrer has created an entirely new way for us to view and interact with materials. Imaging materials down to the atomic level with the STM represents a truly remarkable feat of scientific and technological insight. Moreover, the demonstrated capabilities of the STM to actually control materials properties on the atomic and nanometer levels opens new doors to exciting science and technology at the quantum level, which previously could only be considered in textbook equations and gedankenexperiments. The fact that, over the past thirteen years, the STM and related instruments, notably the AFM, have led to a vast number of new developments across a wide array of disciplines clearly indicates the timeliness and usefulness of this class of instrumentation. This monograph is the product of an extended review article, which I was asked to write for Volume 2 of the series Materials Science and Technology:A Comprehensive Treatment, edited by Robert W. Cahn, Peter Haasen, and Edward J. Kramer (Volume Editor Dr. Eric Lifshin). It began with the aim of describing the use of the STM by example, using a host of demonstrated applications. In the light of the rapidly increasing literature on these subjects and related topics, as the manuscript was being written, the work was extended to cover AFM with brief expositions of nanoscale modification and techniques spun-off from STM technology. In this work, I have attempted to describe a wide array of benchmark experiments and relevant examples and extensions of the capabilities which these made available. I have, therefore, included references to work in physics, chemistry, materials science, biological science, and metrology. The descriptions are by no means exhaustive, but the extensive set of references will hopefully allow the reader to pursue topics of interest in more detail. In addition, considering the explosion of work in the field, several examples of equal importance to those used were not included simply due to lack of space and time. One primary intent is that the reader will gain an appreciation for the diverse fields in which these techniques have established themselves. The photographs on the opposite page are intended to give the reader a taste of the power and beauty of STM and AFM imaging. I wish to acknowledge the authors whose work has been included in this monograph and their publishers. I am indebted to the editorial and production staff at VCH for their contribution to the task of assembling this monograph. My particular thanks go to Dr. Peter Gregory, Dr. Ute Anton, and Ms. Deborah Hollis on the editoral side and to Wirt.-Ing. Hans-Jochen Schmitt on the production side. March 1994

N. John DiNardo


Biography

Professor DiNardo is Associate Professor of Physics at Drexel University and Adjunct Associate Professor of Materials Science and Engineering at the University of Pennsylvania. He received his Ph. D. in Physics in 1982from the University of Pennsylvania. His dissertation involved the use of Electron Energy Loss Spectroscopy (EELS) to study the vibrational structure of adsorbate-metal systems. Subsequently, as a Postdoctoral Fellow at IBM Research (Yorktown Heights), he studied the relationship between vibrational and electronic structure of metal, semiconductor, and polymer interfaces with EELS, Photoelectron Spectroscopy, and Low Energy Electron Diffraction. As a member of the faculty of the Department of Physics and Atmospheric Science at Drexel University since 1984, Professor DiNardo, along with his students, has instituted a program to study the properties of semiconductor surfaces and metal-semiconductor interfaces. A primary area of focus has been the characterization of the semiconductorto-metal transition using ultrathin alkali-metal films on Si and GaAs surfaces with an array of complementary experimental techniques. Currently, his work extends to vibrational spectroscopy of semiconductor and polymer surfaces, variable-temperature STWSTS of semiconductor interfaces, and the characterization of the geometric and electronic structure of diamond films with STM and AFM.



.

N John DiNardo

Department of Physics and Atmospheric Science. Drexel University. Philadelphia. PA. U.S.A.

List of Symbols and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Introduction ....................................................... Scanning Tunneling Microscopy (STM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.1 Historical Perspective .............................................. 2.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 Electron Tunneling and STM Imaging ................................ 2.2.2 Scanning Tunneling Spectroscopy (STS) .............................. 2.2.3 Inelastic Tunneling Spectroscopy .................................... 2.2.4 Ballistic Electron Emission Microscopy (BEEM) ....................... 2.3 Instrumentation ................................................... 2.3.1 Microscope Design: STM Heads .................................... 2.3.2 Tips . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Vibration and Shock Isolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.4 Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.5 Microcomputer Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Semiconductor Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Si(ll1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2 Si(100) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.3 GaAs(ll0) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.4 Photoinduced Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Metal- Semiconductor Interfaces .................................... 2.5.1 Alkali-Metal- Semiconductor Interfaces ............................... 2.5.2 Growth of Trivalent Metals on Si(OO1) ............................... 2.5.3 Ambiguities in Structural Determinations ............................. 2.5.4 Electron Localization at Defects in Epitaxial Layers .................... 2.5.5 E , Pinning, Mid-Gap States, and Metallization ........................ 2.5.6 The Insulator + Metal Transition in Metallic Fe Clusters Grown on Semiconductor Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.7 Microscopy and Spectroscopy of Buried Interfaces - BEEM . . . . . . . . . . . . . 2.6 Metal Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.1 Close-Packed Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.2 Surface Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.3 Stepped Surfaces .................................................. 2.6.4 Adsorbate-Induced Reconstructions of Metal Surfaces . . . . . . . . . . . . . . . . . . 2.6.5 Growth of Metallic Adlayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 6 12 12 16 17 22 27 29 31 32 38 39 40 43 43 43 47 50 50 51 52 53 54 56 58 60 60 64 66 67 68 70 74

2 2.6.6 2.7 2.8 2.9 2.10 2.11 2.1 1.1 2.1 1.2 2.12 2.13 2.14 3 3.1 3.1.1 3.1.2 3.1.3 3.1.4 3.1.5 3.1.6 3.1.7 3.2 3.3 3.4 3.4.1 3.4.2 3.4.3 4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 5

5.1 5.2 5.3 5.4 5.5 5.6 6 7


Resistivity in Polycrystalline Metals - Scanning Tunneling Potentiometry . . . Insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Layered Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Charge Density Wave Systems ....................................... Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Molecular Films, Adsorbates, and Surface Chemistry . . . . . . . . . . . . . . . . . . . Molecular Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Adsorption and Surface Chemistry ................................... Electrochemistry at Liquid-Solid Interfaces ........................... Biological Systems ................................................. Metrological Applications .......................................... Atomic Force Microscopy ........................................... Atomic Force Imaging ............................................. Graphite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Insulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polymer Surfaces and Metal Films on Polymer Substrates . . . . . . . . . . . . . . Biological Molecules ............................................... Adsorption Dynamics of Biological Molecules in Real Time . . . . . . . . . . . . . Nanoscale Surface Forces ........................................... Nanotribology .................................................... Non-Contact Imaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Van der Waals Forces .............................................. Electrostatic Forces ................................................ Magnetic Forces .................................................. Manipulation of Atoms and Atom Clusters on the Nanoscale . . . . . . . . . . . . . Transfer of Atoms and Atom Clusters Between Tip and Sample . . . . . . . . . . Tip-Induced Lateral Motion of Atoms on Surfaces ..................... Nanoscale Modification by Tip-Induced Local Electron-Stimulated Desorption ....................................................... Nanoscale Chemical Modification ................................... High-Temperature Nanofabrication .................................. Nanoscale Surface Modification Using the AFM ....................... Towards Nanoscale Devices ......................................... Spin-offs of STM - Non-Contact Nanoscale Probes . . . . . . . . . . . . . . . . . . . . Scanning Near-Field Optical Microscope (SNOM) ..................... Photon Scanning Tunneling Microscope (PSTM) ....................... Scanning Thermal Profiler (STP) .................................... Scanning Chemical Potential Microscope (SCPM) ...................... Optical Absorption Microscope (OAM) ............................... Scanning Ion Conductance Microscope (SICM) ........................ Acknowledgements ................................................ References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

74 75 79 86 92 96 96 97 108 111 115 118 123 124 125 125 126 127 128 129 130 132 133 133 134 135 137 138 139 141 142 142 142 143 144 144 145 146 147 149 150 151 151

List of Symbols and Abbreviations

3

List of Symbols and Abbreviations constant vibration amplitude lattice direction lattice spacing autocorrelation function sample - tip spacing piezoelectric coefficient energy (tip, sample) Fermi energy transverse energy electronic charge interatomic force force field resonance frequency Planck constant; wall thickness of tube; height mean surface height current collector current tunneling current injected current current density piezoelectric constants force constants wavevector Boltzmann constant interatomic force constant tunneling matrix element between tip wavefunction and sample wavefunction free electron mass atomic mass effective masses tunneling resistance; scattering parameter; radius of curvature of the tip tip radius tippsample separation absolute temperature time bonding energy coulomb energy voltage sample potential Cartesian coordinates tip-sample separation

4


0 0 , wb

corrugation amplitude; energy gap critical angle inverse decay length wavelength Fermi wavelength chemical potential electrical resistivity charge density diameter of orifice set up by a tip atom work function (apparent) barrier height wavefunction of sample, tip surface wavefunction of sample, tip wavefunction in vacuum gap vibrational frequency resonance frequency

AC ADC AES AFM ATP BCS BEEM CBM CDW CFM CITS DAC DAS DB DC DMPE DNA DOS EELS ET FIM GIC H HCT HM HOPG IETS IPES

alternating current analog-to-digital converter Auger electron spectroscopy atomic force microscope; atomic force microscopy adenosine 5’-triphosphate Bardeen-Cooper - Schrieffer ballistic electron emission microscopy conduction band minimum charge density wave charge force microscope current imaging tunneling spectroscopy digital-to-analog converter dimer-adatom-stacking domain boundary direct current dimyristoyl-phosphatidylethanolamine deoxyribonucleic acid density of states electron energy loss spectroscopy embedded trimer field ion microscopy graphite intercalation compound honeycomb hone ycomb-chain-trimer high resolution optical microscope highly oriented pyrolytic graphite inelastic electron tunneling spectroscopy inverse photoelectron spectroscopy

A 9,

x 1 1, P

e e 0.0, t ) em

4, 4m 4s 4 3

4 a

*;

$9 $T

$L

$s(4

*T(4

0

List of Symbols and Abbreviations

JDOS L-B LEED LMIS MFM ML NDR OAM PCM PDS PMMA PSTM PTFE RBS RHEED rms SBH SBZ SCPM SEM SICM SNOM SPV STEM STM STP STS T TEM TTF-TCNQ UHV UPD UPS VBM WF XPS

joint density of states Langmuir - Blodgett low-energy electron diffraction liquid metal ion source magnetic force microscope monolayers (unit) negative differential resistance optical absorption microscope phase contrast microscope photothermal deflection spectroscopy poly(methylmethacry1ate) photon scanning tunneling microscope polytetrafluoroethylene Rutherford backscattering reflective high-energy electron diffraction root mean square Schottky-barrier height surface Brillouin zone scanning chemical potential microscope scanning electron microscope scanning ion conductance microscope scanning near-field optical microscope surface photovoltage scanning transmission electron microscope scanning tunneling microscope; scanning tunneling microscopy scanning thermal profiler scanning tunneling spectroscopy tesla transmission electron microscope tetrathiafulvalene tetracyanoquinodimethane ultra high vacuum underpotential deposition ultraviolet photoelectron spectroscopy valence band maximum wavefunction X-ray photoelectron spectroscopy

5

6


1 Introduction One of the principal objectives in the experimental study of bulk solids is the characterization of atomic structure. Such information is used to provide a link between geometric structure and the other physical properties of a solid. Building upon advances in the experimental and theoretical understanding of the bulk, surfaces and interfaces have been intensively studied in recent years because of their fundamental and technological importance. The surface structure of a single crystal differs from that of the underlying bulk, since truncation at a lattice plane results in the relaxation of the near-surface atomic geometry, often creating unique lateral surface reconstructions. Specific electronic states and vibrational modes can be associated with these structures. The goal of classical surface science is to establish a fundamental atomistic view of surfaces. It is clear that high-technology problems in the current age of materials research rely on such a perspective. Nanotechnology, i.e., the characterization and manipulation of structures on the nanometer scale, is an increasingly important area of research and development (Crandall and Lewis, 1992). For example, the fabrication of microelectronics devices by epitaxial atom-by-atom growth depends on interactions and energetics governed by phenomena on the atomic scale. Thus, diagnostics using ultrahigh resolution microscopy can help to define the proper conditions under which films may be grown with atomic thickness control. To create structures of nanometer lateral dimensions requires new methods to manipulate atoms and molecules at surfaces. In surface chemistry and catalysis, different crystallographic orientations of a surface or different distributions of defects can al-

ter reactivity by orders of magnitude; the structural and electronic origin of these effects is still under study. Beyond classical surface science, processes at liquid-solid interfaces, e.g. in electrochemical cells, may also be studied at the atomic level. In the new age of structural biology, biological molecules or systems, deposited on a substrate, may likewise be imaged at this level to ascertain critical information on the geometric and electronic structure. Atomic-scale forces between materials at an interface are important in areas of tribology and adhesion. These are areas where nanoscale properties are directly related to macroscopic phenomena. Likewise, the forces between a sharp tip and a surface can be used for imaging; for example, the repulsive force between a tip and a sample can be exploited to make an atomic scale profilimeter so long as the forces are small enough not to disturb the surface structure. While the size scales of the structures under consideration range from that of individual atoms to tens of nanometers and beyond, it is clear that atomic resolution is not required for all applications. Surface science has developed as a multidisciplinary field over the past 30 years to study the physical and chemical properties of solid surfaces and interfaces. Until recently, bulk structural techniques, such as transmission electron microscopy or x-ray diffraction, have lacked the sensitivity to view surfaces at atomic resolution, and these techniques still require rather stringent sample preparation procedures and/ or experimental set-ups. Many techniques have been developed involving particle scattering or emission to probe the atomic, electronic, and vibrational structure of surfaces since the small mean free path of particles, electrons, ions, or atoms maximizes surface sensitivity. Measurements have typically been performed under high-vac-

7

1 Introduction

uum or ultrahigh-vacuum conditions in order to preserve surface cleanliness and as a necessary condition to operate particle beam experiments. The major drawback of such spatially-extended probe beam techniques is that the data represents an average over macroscopic areas of the surface (with respect to atomic dimensions) so that the effects of inhomogeneities, which may occur over atomic distances, are often impossible to isolate. Even high-quality single crystal surfaces are not atomically perfect. Steps, defects and other irregularities may produce important effects which cannot be isolated by averaging over a large area. “Real” surfaces - those used in technological applications are somewhat removed from the single crystal norm of surface scientists, typically possessing more disorder, defects, crystalline, grains, impurities, etc. It is important to understand the way in which these undesirable structures might undermine the effectiveness of the material for specific applications. Thus, as a complement to the information that can be derived from established techniques, real-space views of surface geometry and spectroscopic capabilities at atomic resolution, can provide a means for comparison with theoretical calculations at the atomic level. The invention of the scanning tunneling microscope (STM) in 1982 (Binnig et al., 1982a, b) made it possible to probe surfaces on the nanometer scale, since the STM can relate geometry and electronic structure at surfaces atom-by-atom. Significantly, the capability of the tunneling probe to operate in liquid and gaseous environments, as well as in vacuum, allows direct analysis of processes at liquid -solid interfaces and of biological structures and processes in vivo. Recognizing that electron tunneling occurs across a small gap, we see that interatomic forces become intimately related to such

measurements. This fact has allowed STM technology to be applied to atomic forces measurements at a level of sensitivity of < N by the invention of the atomic force microscope (AFM) (Binnig et al., 1986). Furthermore, the ability to fabricate a microscope probe and control it with nanometer precision has inspired a number of novel allied scanning microprobe techniques (Wickramasinghe, 1990). With the prospect of further device miniaturization on the nanometer scale, the ability of the STM to manipulate atoms and clusters to fabricate microscopic structures and subsequently analyze these structures with the same probe has also been demonstrated, and the microscopic mechanisms for such nanoscale processing are still being studied. STM possesses a distinct advantage over other microscopy techniques in both vertical and lateral resolution, as seen in Fig. 1. Its application to a vast variety of materi-

106

-

5

y 4

104

v)

-I

p

102

(I

w

> i ’

I 1

1

I

to2

I

I

lo4

I

I

I

to6

LATERAL !XALE (1) Figure 1. Resolution of various microscopes - HM: high resolution optical microscope; PCM: phase contrast microscope; (S)TEM: (scanning) transmission electron microscope; SEM: scanning electron microscope; FIM: field ion microscope, etc. (Kuk and Silverman, 1989).

8


als problems and its extension towards the development of allied techniques has occurred over a remarkably short time, and this points to the engineering triumphs which the instrument itself and associated hardware and software represent. Prior to the development of STM, only specialized techniques such as field ion microscopy could provide direct atomic resolution images of surfaces. Atomic resolution with electron microscopy is constrained by sample preparation thereby limiting the range of applicability of the technique. Among other recent developments, real-space imaging of surfaces using electron holography has been reported but limitations still exist for imaging non-periodic structures. The basic principle of the STM is illustrated in Fig. 2. An atomically-sharp tip, biased with respect to the sample, is positioned at a distance of I1081 from the sample surface. A current in the nanoampere range passes between the tip and the sample due to electron tunneling through the vacuum barrier in the gap region. The

CONSTANT CURRENT MODE SCAN

Figure 2. Schematic representation of the operating concept of an STM operating in the constant current mode or the constant height mode (Hansma and Tersoff, 1987).

current decreases exponentially as the gap distance increases. The tip motion is controlled in three dimensions by piezoelectric transducers that distort by applying a voltage (electric field) across them. A bias of 1V across a typical piezoelectric element may cause an expansion or concenlOA, so that sub-atomic tration of movement of the tip can easily be obtained. It can be assumed that electronic states (orbitals) are localized at each atomic site, so measuring the response of the tip being scanned over the surface can give a picture of the surface atomic structure. The structure may be mapped in the constant current mode by recording the feedback-controlled motion of the tip up and down, such that a constant tunneling current is maintained at each x-y position. The structure can also be mapped in the constant height mode by recording the modulation of the tunneling current as a function of position, while the tip remains a constant height above the surface. The latter mode is preferred for scanning at high speeds but can only be used on very smooth surfaces. The former is required to obtain topographic images of rough surfaces. Figure 3 shows a schematic diagram of the first STM of Binnig and Rohrer, where the tip is mounted on a piezoelectric tripod assembly, and the sample (S) is mounted on a “louse” (L). The louse is a device which can “walk” the tip on the base by sequences of electrostatic clamping and piezoelectric distortions. The ability to image the electronic structure is a natural byproduct of STM, and this provides a natural means of obtaining spatially-resolved spectroscopic images. As in tunneling spectroscopy at metal -oxide-metal junctions (Giaver, 1960), electrons pass from filled electronic states (or bands) to unoccupied states (or bands). Depending on the sign of the tunneling bias, N

-

1 Introduction

I/

1

the current can be directed from sampleto-tip or vice-versa. An illustration of this feature of the STM is given in Fig. 4,which shows two images of the same region of a GaAs(110) surface with biases of opposite polarities (Feenstra et al., 1987b). The positive bias image is displaced from the negative bias image due to the localized atomic orbitals accessible to tunneling. In particular, rehybridization to sp2-like bonding and relaxation occur at this cleavage plane due to the truncation of the bulk. A filled lone-pair band is localized above As atoms, while an unoccupied band is associated with the Ga atoms. The tunneling current is maximized over As atoms when scanning with a tip bias of + 1.9 V, while the current is maximized over Ga atoms with a tip bias of - 1.9 V. Stopping at one particular location and scanning the tip bias measures the local ('joint) density of states of the sample and tip. The most general use of the STM is for topographic imaging not necessarily at the atomic level but on length scales from < 10 nm to 2 1 pm.Figure 5 shows an ap-

7

9

Figure 3. A schematic diagram of the IBM Zurich-design microscope of Binnig and Rohrer showing the piezo tripod, louse, tip, and sample holder (Binnig and Rohrer, 1983).

plication related to mesoscopic physics and an application in practical surface metrology (Denley, 1990).In the first example, an STM was used to measure the surface morphology of quantum dots. As can be seen, the dots are arranged in a periodic

.

.

3%

Figure 4. Two views (a, b) of a GaAs(110) surface taken at biases with opposite polarities. With the tip biased positive with respect to the sample, occupied lone-pair states at As sites are imaged; the opposite bias produces a laterally-shifted image of the unoccupied orbitals at Ga sites. (Feenstra et al., 1987b).

10


Figure 5. (a) STM image of an array of 100 nm high quantum dots on GaAs; (b) STM image of a compact disc surface (Denley, 1900).

array on GaAs, are each separated by -300nm, and are -100nm in height. The second example shows the surface of a compact disc over a 6 x 6 pm area. As an offshoot of STM technology, the atomic force microscope (AFM) provides a means to image surfaces by direct (or proximal) contact of a sharp tip with a surface.

Insulating substrates and organic films are more amenable to AFM imaging because a conducting substrate is not required. In an AFM, a sharp tip is mounted on a cantilever and is typically in contact with the surface while the deflection of the cantilever - the force - is monitored optically or by other means. The contact force is

11

1 Introduction

typically c N ; in constant force operation, the piezoelectrically-actuated sample height modulation in response to hold the cantilever deflection fixed is plotted as a function of (x, y) to form an image. AFM can measure structures with atomic resolution, and new, high-aspect-ratio tips permit imaging of deeply channeled structures (Keller and Chih-Chung, 1992). Examples of the imaging capabilities of the AFM range from atomic resolution imaging of graphite (Fig. 6) (Rugar and Hansma, 1990)to obtaining larger scale views of step structures on an annealed Si surfaces (Fig. 7) (Suzuki et al., 1992) to the visualization of organic layers (Fig. 8) (Garnaes et al., 1992). The highly oriented pyrolytic graphite (HOPG) surface as well as other layered materials have seen widespread use in STM and AFM studies for instrument calibration and as thin film substrates, since clean, flat, inert surfaces can be prepared by simply cleaving in air. The image of the HOPG surface shown in Fig. 6 demonstrates that the AFM can provide the same high lateral resolution as STM. Furthermore, it should be noted that the symmetry of a graphite image taken with an STM differs from that taken with an AFM because the STM probes the electronic structure, while the AFM “feels” the repulsive interaction between tip and surface. On a larger scale, the AFM has been used to determine the organization of steps on annealed vicinal Si surfaces. DC heating of Si surfaces flashed to 1200°C followed by annealing around the (1 x 1) (7 x 7) transition temperature (T,x 885 “C) had previously resulted in the bunching of steps. The microstructure of these regions obtained by AFM in air, after annealing above or below T, in ultrahigh vacuum, is shown in Fig. 7 (Suzuki et al., 1992). Step-band regions, interspersed by ter-

Figure6. AFM image of a graphite surface; the C atoms are separated by 1.5 A (Rugar and Hansma, 1990).

__ 4---

-

[ I 171

J

I

l.il

Figure 7. AFM images of vicinal Si(ll1) surfaces flashed to 1200°C and annealed at 895°C for 5 min (a), or at 875°C for 5 min (b), showing step-bunching structures (Sumki et al., 1992).

12


races, are of the order of 1 pm in width. Annealing below T, results in the formation of a large number of sub-step-bands, each several monatomic steps high. These make up the step-band, and the density of sub-steps is higher in the middle than on the sides. At the edges, a curvature of the terraces is observed. Annealing above T, gives a small number of discontinuous step structures with sharp transitions to the terraces. In both cases, the terrace structures are similar. The curvature obtained at lower temperatures arises due to the formation of sub-step-bands, and is associated with the fact that the (1 x 1) * (7 x 7) transition occurs at lower temperatures for larger misorientation angles. Imaging surfaces of polymer films with AFM provides information on polymer branching, conformation, and intermolecular interactions, without the requirement for electrical conductivity associated with STM imaging. Due to several possible technological applications of Langmuir Blodgett films at the sub-micron to nanoscale regimes, their molecular structure and packing is a topic of central interest. Figure 8 shows the structure of a four-layer film of cadmium arachidate in which terminal methyl groups exhibiting a height corrugation of < 0.2 nm are imaged (Garnaes et al., 1992). The observed boundary between two distinct ordered domains is found to be misoriented by 60" and the lattice structure is preserved almost to the edge of the boundary. The fact that such ordering is observed leads to the conclusion that the misorientation is due to hexagonal twinning. In addition, the AFM could detect a larger scale buckling in these films which appears to be an equilibrium superstructure. Here the techniques of STM and AFM are reviewed by discussing applications in surface science and extensions to other sci-

-

Figure 8. 17.5 x 17.5 nm2 AFM images of cadmium arachidate Langmuir-Blodgett films. The dashed line shows the boundary between two domains misoriented by 60" (Garnaes et al., 1992).

-

entific and technological areas in the first two sections. For both microscopies, we begin with a brief historical perspective and cover the theoretical and instrumental issues. The discussion is followed by a section that reviews some of the uses of these techniques for nanoscale manipulation, followed by a section that describes complementary scanning probe techniques based on the design and measurement philosophies of STM.

2 Scanning Tunneling Microscopy (STM) 2.1 Historical Perspective The major set of advances that led to the invention of the STM was the solution of three long-standing experimental problems. First, although theory could explain the physics of tunneling across a vacuum gap, obtaining the stability necessary to maintain a gap of the order of a few

2 Scanning Tunneling Microscopy (STM)

angstroms had not yet been demonstrated. Previously, tunneling measurements were performed using thin, rigid insulating junctions between metal electrodes. Second, the technology to position and scan a probe over a surface with sub-angstrom precision was available using piezoelectric transducers but needed to be refined for this application. Third, a methodology had to be created to bring a sample starting far away from the tip to within 5 8, without damaging the tip or the sample. This was first accomplished by using a piezoelectric/electrostatic “louse” for coarse approach and the z-piezoelectric transducers for fine zmotion (Binnig et al., 1982a). The invention of the STM was preceded by experiments to develop a surface imaging technique whereby a non-contacting tip would scan a surface under feedback control of a field emission current between tip and sample. The manifestation of this concept led to the invention of the Topografner developed at the National Bureau of Standards (NBS, presently National Institute of Standards and Technology) in the late 1960s (Young et al., 1972). The final Topografiner design was remarkably similar to that of the STM ultimately invented by Binnig and Rohrer over 10 years later (Binnig et al., 1982a, b). At NBS the goal was to develop an instrument for sub-micron scale metrology of surfaces - essentially a non-contacting, high-precision stylus profilimeter. The Topografiner (Fig. 9a) used a sharp, mechanically-etched tungsten tip which was scanned about 1008, above the surface with a sufficiently high bias to operate in the field-emission regime with electron current flowing from tip to sample. Feedback control of the vertical piezoelectric actuators was implemented to maintain constant emission current, and the surface topography was obtained by using the z-piezo bias (z-drive voltage) for

-

13

height as a function of the ramped x- and y-drive voltages. The concept was demonstrated as workable, as illustrated by Fig. 9 b, where the topographic profile of a diffraction grating was mapped. However, the Topografiner was plagued by stability problems due to the difficulty of suppressing vibrations causing instabilities in the tip-sample separation. In their original paper (Young et al., 1972),however, the authors envisioned the eventual progression to imaging in either the field-emission or vacuum tunneling regimes. Curves of current versus separation from the field emission to point contact regimes were measured at various biases. Around the same time, parallel experiments performed at IBM (Thompson and Hanrahan, 1976) using thermal drives and lead whiskers were directed at similar goals. In a 1982 paper appearing in Applied Physics Letters, Binnig and Rohrer reported the first observation of electron tunneling across a stable vacuum gap for several different tip-sample biases (Binnig et al., 1982b). The vibration problems had been solved by mounting the STM on a magnetically-levitated platform, as seen in Fig. 10, to decouple high-frequencies with the vacuum system resting on a massive bench supported by air cushions. A tungsten tip mounted on a piezoelectric transducer was used to approach a platinum surface, and the exponential dependence of current versus gap separation over four orders of magnitude was observed. This data, reproduced in Fig. 1 1, confirmed that vacuum tunneling had been achieved. Using the Fowler-Nordheim expression for tunneling resistance, R, as a function of separation, s, R (s)x exp ( A + ‘ I 2 s) A = 1.025eV-

(1)

’,

8,- work function values

4 z 3.5 eV were obtained for moderately

14

, -


VACUUM C H A Y I E R

A

f

400

I

I

I SCAN VOLTAGE

2-PIE20 VOLTAGE

I

I 1

‘

-

./

-I- - ’ I

‘

I

CONSTANT CURRENT PS

l

FILTER

-L

T

1-I

.

RECORDER

Figure 9. (a) Schematic diagram of the Topografiner; (b) topographic view of a 180 line/mm daraction grating replica obtained in the FIM mode (Young et al., 1972).

- Pb ‘T ‘ R

Figure 10. First tunneling unit mounted on magnetic levitation system. The tungsten tip (W) was fixed on a support (A) set on a piezoplate (PP). The electrostatic clamping mechanism consists of feet (F),dielecttric sheets (D) and the metal plate (MP). Magnets (M) mounted on the base of the tunneling unit are repelled by the liquid-helium-cooled lead bowl (Pb) (Binnig et al., 1982a).


15

Figure 11. Tunneling resistance (left axis) and tunneling current (right axis) versus vertical displacement of a tip providing first evidence of vacuum tunneling k,. ’ . ’ ... , 1982b). . (Binnig et al., ,

-

’

”

Di8placrmmt of W l i p

4

[ I d = lA]

”

clean Pt surfaces. Since metal -insulator metal tunneling typically gave barriers of < 1 eV, the measured value of 4 confirmed vacuum tunneling. All the essential elements were in place to scan and image, and, in their closing statements, Binnig and Rohrer stated their goal to apply vacuum tunneling as a method for spatially-resolved imaging and electron spectroscopy. Shortly thereafter, Binnig and Rohrer demonstrated the STM as an atomic-resolution microscope with images of monoatomic steps and reconstructions of the CaIrSn,(llO) and Au(ll0) (Binnig et al., 1982a) surfaces, and the first real-space images of the Si(111)-7 x 7 surface (Binnig et al., 1983b), as shown in Fig. 12. Imaging was accomplished by scanning the tip over the samples while maintaining a constant tunneling current using feedback to control the tip-sample distance. Coarse approach was accomplished by means of a “louse”, or piezoelectric-electrostatic walker (Fig. 3). A piezoplate rests with three metal feet insulated from a metal base by a

high-dielectric constant material. The feet were clamped on the plate by a high electric field so that elongation and contraction of the piezoplate with an appropriate foot clamping sequence provided for movement in two dimensions. The image of the Si(ll1)-7x 7 surface shown in Fig. 12a is a plot of the z-piezo voltage as a function of x and y positions obtained with a chart recorder. The gray scale image depicts 12 Si adatoms in each unit cell, which are the basis for the reconstruction. The impact of such a capability was immediately evident. For example, the structure of the Si(l11)-7 x 7 surface had been a puzzle for over 20 years. Complemented by TEM studies (Takayanagi et al., 1985), this work and subsequent studies provided key information to finally arrive at the actual structure, which is discussed in greater detail in a later section.

16


(a)

Figure 12. First topographic image of the Si(ll1)7 x 7 surface presented as (a) a topographic relief map and (b) a top-view gray-scale map. (c) The structural model based on these observations (Binnig et al., 1983 b).

2.2 Theory

The most striking aspect of an STM image is that features separated by distances of the order of an interatomic spacing can be resolved. Such features are often taken to represent the position of atoms, and, to the extent that this is true, the STM may be viewed as a tool for measuring the atomic structure of surfaces. However, taking this view without paying attention to the electronic structure has proven to be dangerous for a number of structures. Upon consideration of the tunneling process and the nature of electronic states at the surface and the tip however, it is clear that an STM image really represents spatial variations of the local electronic structure and tunneling barrier at the surface. Our previous comparison of two images of the GaAs(ll0) surface obtained with biases of opposite polarities (Fig. 4) clearly demonstrated the importance of spectroscopic effects in image interpretation. From this fact it follows

that atomically-resolved electronic (and vibrational) spectra can be obtained by acquiring I - V profiles at various locations within a surface unit cell of clean well-ordered regions or in the vicinity of defects or adsorbates, so that a map of electronic states at the surface can be derived. Here, tunneling between two conductors in one dimension is considered and extended to three dimensions to reflect the geometry of a spherical tip above a corrugated conducting surface. We also consider the transition from the tunneling to the point contact regime, and operation at high biases in field-emission for which electron interferometry is observed. The discussion will address details of the electronic structure of the sample and the tip, so as to understand spatial imaging of localized electronic states at surfaces, including considerations of local inelastic tunneling and ballistic electron emission microscopy (BEEM), where spatial and


spectroscopic details of buried interfaces can be obtained.

- -4-- I,

/I 1-

17

Lcuum

2.2.1 Electron Tunneling and STM Imaging

Depending on the imaging mode at a given tip bias, an STM image is a map of the z-height of the tip above the surface needed to maintain a constant tunneling current (constant current mode), or of the tunneling current while the tip is scanned at a constant height above the surface (constant height mode). Theoretical models of the tunneling probability provide an understanding of the observed spatial resolution and spectroscopic aspects of STM. The first theoretical discussion of tunneling from a point electrode was presented by Tersoff and Hamann (1983), which was based on the earlier work of Bardeen (1961). Development of the one-dimensional formalism begins with the calculation of the tunneling current between the wavefunctions (WFs) of a metal tip (T) and a metal surface (S), as depicted in Fig. 13. The geometry for the calculation is shown in Fig. 14. In first-order perturbation theory,

I=

~

2ne h

x f ( E T )[1-f(ES+ev)11MTS12' TS

-6(E,-E,)

SAMPLE

TIP

Figure 13. Energy level diagrams of the sample and the tip: (a) with the sample and tip independent, the vacuum levels are equal; (b) with the sample and tip connected with no potential difference, the Fermi levels are equal; (c) application of a negative tip bias, V, < 0, allows electron to flow from occupied states of the tip to unoccupied states at the sample surface; (d) application of a negative sample bias, V, > 0, allows electrons to flow from occupied states of the sample surface to unoccupied states in the tip (Hamers 1989).

(2 a)

where

i.e., f(E)is the Fermi function, I/ is the applied voltage, M,, the tunneling matrix element between the tip WF($T) and the surface W F ( t j s ) , 6 (x) the delta function, Ei the energy of a state in the absence of tunneling (i = T, s),and ,u the chemical potential.

For small tunneling voltages (e.g. -10meV between the tip and the substrate) and low temperatures (k,T 50 meV for T = 300 K), f(E)can be expanded to obtain

-

27c I=-e21/C)MT,126(ET--EF)'

zz

TS

. d(E,-EE,)

(3)

18


The matrix element M,, is obtained from (4) h2 M,, = -~ I d s . ($T* V $ S - $s V4G) 2m

the vacuum gap can be written as

where m is the free electron mass, the integral is taken over a surface lying entirely within the vacuum barrier region between the tip and the sample, * denotes the complex conjugate, and

where x is the inverse decay length, i.e.,

a

a

a

ax

ay

aZ

V=i-+j-+k-

Carrying out the integral in one dimension (plane waves) by taking $! and as the wavefunctions of the tip and the sample, respectively, gives the explicit exponential dependence of the tunneling current as a function of tip-sample separation. In particular, if the tip and sample are identical materials, the wavefunctions in

t+hs(z) =@ ,I e-"

( 5 a)

$,(z) = $;e-x(d-z)

( 5 b)

with 4, the average work function, in electron volts and x in k'. Then the tunneling current exhibits an exponential dependence on the separation d given by

I C C C ~ $l$~12e-2xd :~~

(7)

Continuing with the spherical tip configuration of Fig. 14, M,, may be evaluated to assess the potential spatial resolution of STM. The surface wavefunctions are expanded in plane waves parallel to the surface with decaying amplitude into the vacuum

,-

CaGexp[-(x2+lkll+G12)'/2~]

$ 0 -a-1/2

G

~exp[i(kII+C).x] (8) where Q, is the sample volume, x = ( 2 m 4)'l2/h2, k is the surface wavevector, and G is a two-dimensional reciprocal lattice vector of the surface.

Figure 14. (a) The geometry for tunneling microscopy calculations shows the tip radius, R, and the tip apex-to-sample distance, d. (b) Contours of constant charge density at the Fermi level, e(r, &), are presented for the Au(100) (2 x 1) (left) and Au(100) (3 x 1) surfaces (TersofT and Hamann, 1983).

19


The spherical tip ( R9 k - I ) wavefunctions are expanded in similar form $;=s2,”2

c,xR e”R(xIr-roI)-l

.e-xlr-vol

0.5 0.4

*

(9)

where sZT is the probe volume and R is the radius of curvature of the tip. The resulting matrix element is

where r o is the position of the center of curvature of the tip. The tunneling current is 32n3 e2 V I= 0’ DT(EF)R 2 X - 4 . h

0.1 0 2

4

6

8100 2

4 6 810

d (8, Figure 15. A set of curves depicting the sensitivity to corrugation amplitudes as the tip radius ( I , ) or tipsample separation are increased after a theoretical treatment (Stoll, 1984). This is given by the vertical attenuation plotted as a function of the lateral period.

lated to the density of states e at the surface for energies around E , for a particular tip position. That is, CJ

e (yo, E )

(124

where where q5 is the work function of sample and tip, and DT(EF) is the tip density of states per unit volume. Without using exact wavefunctions for the tip and the surface, the spatial resolution of the STM was approximated by examining the inverse decay length demonstrating a lateral resolution for Au(ll0)2 x 1 of I 5 8, (Tersoff and Hamann, 1983), in agreement with experiment (Binnig et al., 1983a). Another theoretical investigation (Stoll, 1984) of the relation between resolution, tip diameter (24, and tip-sample distance (s) produced a relationship for vertical attenuation versus lateral period, which is depicted in Fig. 15. The vertical attenuation refers to the ratio of the measured corrugation versus the real corrugation of a metal surface for various values of r s. This figure shows quantitatively that, if r +s increases, the instrument has a reduced sensitivity to the surface corrugation, as expected. In addition, for small bias voltages, the tunneling conductance, (r = I / V , can be re-

+

@(rO,E)=C l$S(ro)12 S

6(ES-EF)

(12b)

This observation will become important when spectroscopic capabilities of the STM are discussed below. The Local Barrier Height

The exponential dependence of the tunneling current depends on both the tipsample separation and the local barrier height. Typically, it is assumed that the barrier height is constant over the entire scanned area, but, if an adsorbed patch of impurities changes the work function in a particular region on the sample, the tip will respond to the reduced barrier height and a structure unrelated to the topography will appear in the image. Recognizing that A q5 = d (In I)/ds, the position dependence of the barrier height can be extracted independently during a scan. In the constant current mode, this can be accomplished by modulating the tip distance by As at a frequency higher than the cutoff frequency of

20


the feedback circuit while scanning (Binnig and Rohrer, 1983; Wiesendanger et al., 1987). In this way, the work function analysis and feedback image acquisition are separated. Using lock-in detection of the current signal, d (In Z)/ds provides the desired position-dependent information on the work function in parallel, with the constant current topographic image.

4,o

3 p

I

I

0

2.0

1

3.0

I-

2.0

U 3

-c

1.o

0

Besides tunneling, two conduction regimes exist for close tip-surface distances - electronic contact and point contact. Although these regimes can be modeled theoretically (Lang, 1987b; Ciraci and Tekman, 1989), they are difficult to control in practice because the exact shape of the tip and the degree of the tip interaction with the surface by, e.g., van der Waals or other forces are not well-defined. Defining the separation as between atomic centers, structural instabilities can be assumed to occur when the separation is equal to the sum of the atomic radii. The electronic contact regime refers to distances for which the tip is sufficiently close to the sample to affect the respective wavefunctions; this leads to the appearance of tip-induced energy sub-bands above E , (Binnig et al., 1985).Point contact refers to the collapse of the potential energy barrier with the onset of ballistic transport due to the creation of energy sub-bands below EF. It has been shown experimentally that tunneling at a reduced barrier height can be maintained for close approach until an oscillatory I - V characteristic appears beyond some structural instability (Gimzewski et al., 1987). The I - z characteristic for an iridium tip and a polycrystalline Ag surface, shown in Fig. 16a, exhibits an abrupt increase in tunnel current interpreted as the onset of

4,o

DISTANCE th

The Transition from Tunneling to Point Contact Regimes lo‘

-

7

10’

JZ

N -

a 4

10’

N

(3

loo

lo4

Sm (1) Figure 16. (a) Tunneling current versus tip-sample separation for a clean Ir tip and an Ag surface (Gimzewski et al., 1987). (b) Conductance, G, versus the diameter,em,of the orifice set up by a tip atom for various values of separation,where 1, = 5.23. Quantization steps are predicted at distances of the order of 1 ,the Fermi wavelength (Ciraci and Tekman, 1989).

electrical contact. Analysis of this abrupt change in resistance indicates the contact area of a single atom. Contact can lead to reversible or irreversible local surface modifications. Calculations (Ciraci and Tekman, 1989)for the close approach of an Ag tip (single atom at the vertex) towards an Ag surface show the details of such a transition (Fig. 16b). At a separation of the sum of the atomic radii, the conductance saturates around 2 e2/h, representative of the ballistic transport limit. As the radius of contact increases, steps in the conductance appear. Beyond the point contact

21


regime, the system settles into a more characteristic conductance versus separation curve. However, in the electronic regime, the barrier height is still varying, whereby the first tunneling sub-band dominates the conductance. Density of' States Effects

The effect of electrode densities of states on tunneling images and their spectroscopic signatures was explored by the consideration of the spatial dependence of the tunneling current between a single atom and a planar surface (Lang, 1985) and variations thereof (Lang, 1986, 1987a). The electrodes consisted of an alkali atom adsorbed on a planar jellium surface and a second planar jellium surface (Lang, 1985). For Na adsorbed on jellium it had been established that the Na 3s-level crosses E , and is partially filled due to charge donation from the substrate (Lang and Kohn, 1970). By modeling the details of tunneling for this system, two key results were obtained, as shown in Figs. 17 and 18. First, tunneling current density contours show that electron flow is localized about the adsorbed atom and is significantly enhanced by the protrusion of the atom from the substrate. Second, tunneling current increases with increasing state density in the vicinity of E,. The state densities of an Na adatom and a Ca adatom on jellium are shown in Fig. 17. Figure 18 shows a contour map of j z / j o(where j , is the current density along z and j , is the current density in the absence of an adsorbed atom) for the two substrates separated by 16 %, with the adsorbed Na atom at its computed equilibrium distance. The current density is localized about the adsorbed atom as a result of the state density of the adatoms around E,. Due to the spatial nature of various states, m = 0 (s and p,) states provide the major

ENERGY RELATIVE TO FERMI LEVEL (eV) FOR N~

2.0 1.5 1.0 2 . 0 - l ,

6

6 n

1.5

-

1.0

-

fi t

-t; ciz

8

k 2

0.5

>

v

)

'

o.o

0.5 I

0.0 -0.5 -1.0 -1.5 -2.0 I

I

I

,

-

-2.0 -1.5 -1.0 -0.5 0.0

0.5

1.0

1.5

2.0

ENERGY RELATIVE TO FERMI LEVEL (eV) FOR Ca

BIAS (eV)

Figure 17. Upper panel: the difference in eigenstate density between a metal-adatom system and the bare metal for Ca and Na. The Na 3s and Ca 4s and 3d/4p contributions are observed. Lower panel: calculated curves of (dl/dV)/(I/V) versus V for the Ca/Na system (solid),and with the tip and sample state densities constant (dotted) (Lang, 1986).

contribution to the tunneling current. Ca, as compared to Na, has a greater state density near E,, and results in an increase in current directly above the adatom by a factor of 4 (Lang, 1985). For tunneling at a bias representative of a specific electronic state, the current forming the image will be dominated by that state (and those of lower biases). The effect

-

22


(b) 10

Po-

+:'"-

I

\

I

I

I

I

I

0

10

20 L

30

(BOHRI

0

10

20

30

L (BOHRI

Figure 18. (a) Contour map of j J j 0 for a Na atom protruding from the left electrode. (b) Contour map of j J j o for a Ca atom protruding from the left electrode (Lang, 1985).

of different states on the vertical displacement has been demonstrated by calculations for Na, S, and Mo (Lang, 1987a). It was found that the dominant contributions are for s- and p-states, but that d-states give almost no contribution. In addition, the origin of negative displacements of the tip for regions where there is reduced state density atop an adsorbate were also discussed. Having shown the localized nature of the tunneling current and making an analogy to tunneling spectroscopy of metal-insulator -metal structures, the derivative of the tunneling current as a function of tipsample bias (dZ/dV) can be expected to give a function related to the joint density of states (JDOS) localized within atomic dimensions. Figure 19 shows the result of such a calculation in which (dl/dV)/ (Z/V) is compared for tunneling between a tip and a sample of constant state density and a Ca sample with a constant state density tip. The error as a function of the width of

the electronic state of the sample being probed is found to be smaller with (dZ/dV)/ ( I / V )than with (dZ/dV). (dZ/dV)/(Z/V) is routinely plotted for spectra obtained with the STM.

2.2.2 Scanning lbnneling Spectroscopy (STS) Occupied and Unoccupied States near E , The previous discussion initially considered situations for which the charge density follows the atomic corrugation at the surface. For example, the contour of s-orbitals would reflect the atomic positions of metal surface atoms, but the extended nature of the s-band in the surface plane would result in extremely small corrugation amplitudes. Semiconductors, on the other hand, possess directional covalent bonds; at the surface, these occupied or unoccupied electronic states may extend out into the vacuum and may reside energetically in the bulk and gap. Assuming a


(a)

3.5

1

1

l

~

l

I

l

II

-2.0 -1.5 -1.0 -0.5 0.0 0.5

1.0

1.5

2.0

BIAS leVl

. a

0

1

2

3

FWHM (eVl

Figure 19. (a) Comparison of the calculated density of states as given by the function (dI/dV)/(I/V) for a tip of constant state density and (dotted) a surface with constant state density and (solid) a surface describing the density of states of Ca. (b) The deviations of peak positions of the dl/dV (dashed) and (dI/dV)/(I/V) (solid) with respect to the actual maxima of the density of states (Lang, 1986).

simple metal tip, the tunneling current is derived from states at the sample surface between E , and ( E + e K). With the goal of mapping localized electronic states related to possible reconstructed phases or defects, an appropriate tip-sample bias must be applied so as to “tune into” specific state(s).

23

For simplicity we assume that the metal tip has a fairly constant density of states (DOS). The previously discussed comparison of constant-current images of the GaAs(l10) surface with opposite polarities described the spatial localization of the occupied and unoccupied states at the surface (Feenstra et al., 1987b). As a next step, recording I - I/ relations with the STM by sweeping the bias at each atomic site defines the principle of scanning tunneling spectroscopy (STS). STS allows the measurement of the energy levels at localized positions on the surface, which can be processed to map locations of individual surface electronic states. The use of STM as a local spectroscopic probe (Hamers, 1989; Tromp, 1989)has expanded particularly for the study of semiconductor surfaces and interfaces. Theoretically, the JDOS of tip and sample can be taken into account by explicitly including their functional dependencies in the tunneling matrix element, as previously described (Lang, 1986). In an early treatment of bias-dependent tunneling, the spatial characteristics of G-and n-bands of graphite as a function of tunneling bias were calculated (Selloni et al., 1985). The calculated corrugation amplitudes of individual wavefunctions in the vacuum region demonstrated that discrete states could be imaged by bias-dependent imaging. It was also shown that band structure effects are important. Layered materials such as graphite possess Fermi surface structures at surface Brillouin zone (SBZ) boundaries for which the surface wavefunctions exhibit standing wave solutions. The corresponding STM images of those states do not then reflect atomic positions, and the corrugation amplitudes do not reflect the atomic corrugation. Variations in the slope in an I - I/ profile occur when new states begin to contribute

24


to the tunneling current. The differential conductivity, dZ/dV versus gives a rough picture of the state density. While there is no simple relation between the intensity of these features and the DOS (dZ/dV)/(Z/V), or d (lnZ)/d (In V ) ,versus V better reflects the positions of the maxima in the DOS (Lang, 1986; Feenstra et al., 1987a). It is advantageous to plot (dZ/dV)/(Z/V) for other reasons too, ie., due to the exponential relationship of Z and dZ/dV versus tipsample separation, and because dZ/dVdiverges at zero bias. One means of enhancing sensitivity at low biases is to maintain a junction of constant resistance by reducing the tip-sample distance as the bias is decreased (Feenstra et al., 1987a).

7 1.0

-

3

0.5

-

u

0.0

g

c

I

I

(a)

1

I

Let us first consider spectra obtained with the STM tip above one point on a surface, as illustrated by the family of Z - V curves obtained from an Si(l11)-2 x 1 surface for various tip-sample separations in Fig. 20. Several observations should be noted. (1)Zero conductance is observed for a region consistent with the width of the surface band gap, particularly at the minimum tip-sample separation. (2) The I - V curves exhibit rectifying behavior; i.e., the current for positive sample bias is greater than for negative bias. (3) At constant current, the separation versus bias curves exhibit ripples above _+4eV.The surface band gap in the Si(111)-2x 1 surface is derived from vertical transitions between

-

I

a b c d e f g h ~l k l m

-

4

i

5

-0.5 -

b-

5

Figure 20. (a) Scanning tunneling spectra of the Si(ll1)-2x 1 surface as a function of tunneling distance with the (x, y) position of the tip fixed. Tip sample separations range from 7.8 A to 19.5 A for the spectra a through m. (b) The separations were obtained by measurement of separation versus voltage to maintain a 1 nA tunneling current. Theoretical calculations (dashed lines) used the tip geometry given in (c) (Feenstra et al., 1987a).

20

4

-

6

4

-

2

0

2

SAMPLE VOCTAGE (VI

4

6

8


the n surface bands at the surface Brillouin zone (SBZ). States away from the center of the SBZ decay rapidly into the vacuum; thus, if states at the SBZ center exist, they dominate the tunneling. For Si(l11)-2 x 1, the tip must sample non-zero qll (electron wavenumber parallel to the surface), and this ability depends on the magnitude of the inverse decay length, k , which is a function of the tip-sample separation and bias voltage. The value of the inverse decay length is > 1 A-’ for biases < 1 V, so that the corner of the SBZ can indeed be probed. This rectifying behavior can be explained by the effect of the enhancement of the electric field by the tip, which effectively lowers the potential barrier for tunneling into unoccupied states of Si. The barrier resonances occur due to interferometric effects of free electrons at high bias. When the tip is scanned, a comparison of spectroscopic images over a wide range of sample biases can provide a picture of localized states at the surface. A conductance image was first obtained with an STM on Si(111)-7x 7 by modulating the tip-sample bias around the imaging tunneling bias and using lock-in detection to man dZ/dV (Binnig and Rohrer, 1986). Such images depend on the average bias since this controls the z-height through the feedback loop. Current imaging tunneling spectroscopy (CITS) is an alternative method to obtain spectroscopic images using tip-to-sample reference heights at each position determined by the constant-current imaging bias (Hamers et al., 1986~). This bias is chosen such that it is not overly sensitive to particular surface states. A sample-hold circuit is employed so that, for each pixel, the tunneling current for a series of discrete bias voltages is acquired. Displaying current images at this point only provides indirect information about the surface electronic structure similar to

25

the difficulty in interpreting constant-current images for different biases. However, if diflerences between current images can be displayed, it is possible to display individual electronic states. In fact, if differences between the logarithm of current images for two adjacent biases are plotted, a density of states image midway between the biases is obtained. The choice of the imaging bias still affects the CITS images, and CITS images for a variety of imaging biases typically need to be compared to normalize out this effect. The first demonstration of CITS provided a dramatic and conclusive local picture of the origin of the surface states representative of the Si(ll1)-7 x 7 surface (Hamers et al., 1986~).Previously photoemission (Himpsel and Fauster, 1984) and inverse photoemission (Fauster and Himpsel, 1983; Himpsel and Fauster, 1984) experiments had produced the energy position of these states, but, being techniques that average over the surface, the nature of the electronic states was inferred indirectly. Figure 21 shows three current images obtained for 0.15 < V, < 0.65 V, 0.60 < < 1.O V, and 1.6 < r/; < 2.0 V. The three CITS images are different because they each map different surface states - the adatom state, the dangling bond state, and the backbond state, respectively. To further illustrate this assignment, a comparison of CITS spectra taken at different locations in a 7 x 7 unit cell is also shown in Fig. 21. The “average” of these spectra follows ultraviolet photoelectron spectroscopy (UPS) and inverse photoelectron spectroscopy (IPES) spectra and the position-dependent spectra show the origin of each spectral feature. CITS images, as well as STM images obtained at low biases, show that the faulted and unfaulted halves of the 7 x 7 unit cell appear different. This shows the contribution of the stacking sequence in defining the elec-

Nanoscale Characterization of Surfaces and Interfaces I

I

I

I

I

I

1

I

I

I

I

I

I

10

15

0

-

I

-2.0

-1.5

-1.0

-0.5 00 0 5 ENERGY RELATIVE TO E, lev1

2 0

(e) Figure 21. (a)-(c) Local spectroscopic images of the Si(lll)-7 x 7 surface obtained in the CITS mode: (a) 0.15 V < < 0.65 V; (b) 0.60 V < C: < 1.0 V; (c) 1.6 V < r/; < 2.0 V. (d) Position-dependent CJTS spectra compared with (e) photoemission (solid curve) and inverse photoemission (dashed curve) spectra (Hamers et al., 1986 c).

tronic structure. Similarities in CITS images for both polarities at low bias support the prediction of a metallic state. Observation of the dangling bond states between the adatoms provided further support for the dimer-adatom-stacking (DAS) model (Takayanagi et al., 1985), which contains dangling bonds beneath the adatom layer that are involved in the surface chemistry at the Si(ll1)-7x 7 surface. Measuring electronic spectra with atomic resolution in real space removes the difficulty in separating the contributions of local defects from the intrinsic electronic

structure of the ideal ordered surface. For example, Fig. 22 shows a set of spectra taken at adjacent sites near a defect along a dimer row of an Si(l11)-2x 1 surface (Hamers, 1989). The Si(100) surface is discussed in greater detail in the following section. The gap is decreased close to the defect, with the greatest effect at the defect site itself. This example of spatially-resolved spectroscopy immediately reveals that the defect induces electronic states at E,, resulting in metallic areas separated by semiconducting regions.


Figure 22. Constant current images of the Si(100)2 x 1 surface showing the dimer bond between atoms in the occupied state topographic image (V,= 1.6 V), and the localization of charge about the dimer atoms in the unoccupied state current image (V,= - 1.6 V) (Hamers, 1989).

Spectroscopy at Higher Biases

Surface electronic states, called image states, are bound states that reflect the response of the substrate in the presence of electrons near the surface. These states are modified by the translational invariance along the surface and the reflective properties of the surface, but form a hydrogenlike series of energies given by Efl= Efl + Efl,corr +

h2k2

2m,*

(11-13)

where n is the principal quantum number, is the hydrogenic component of the binding energy, E f l corr , reflects deviations from free electron motion, rn, is the effective mass, and k is the parallel wavevector. One response of the substrate to the biased tip is the creation of an image charge distribution which results in an attractive force between tip and sample (Binnig et al., 1984). In addition, the strong electric field in the gap modifies the image state spectrum by increasing the separation between the levels and extending the image states well above the vacuum level (Binnig et al., 1985). It was shown (Binnig et al., 1985) that these states are observable for high E,

27

sample biases as strong peaks in the tunneling conductance for metal and semiconductor surfaces. These peaks were shown to follow the expected modified hydrogenic progression extending several eV above the vacuum level. In addition, the peaks shift as a function of field strength (varying the gap), whereby inverse photoemission would correspond to the zero-field limit of the image state spectrum. For biases in the field-emission regime, where the electron energy is greater than the tunneling barrier height, standing waves can form in the barrier. As a result, the STM acts as an electron interferometer, whereby structure in the tunneling conductance occurs as a function of electron kinetic energy and/or tip-sample separation (Becker et al., 1985a). This is seen in Fig. 23 where the conductance and gap distance between a W tip and an Au surface is plotted versus bias voltage at constant tunneling current to provide a wide dynamic range. Eleven oscillations in dZ/dV are observed corresponding to standing wave solutions of the electron wavefunctions in the gap, and these were modeled with and without image effects. Beyond the fundamental quantum mechanics of this observation, such measurements are significant because they provide means to obtain the work function and the absolute tip-sample separation. Electron standing-wave interferometry can not only be used between tip and sample but has also been used to form standing waves in ultrathin films to provide contrast at a buried interface. This has been demonstrated for ultrathin Nisi, films grown on Si(l11) (Kubby and Greene, 1992).

2.2.3 Inelastic Tunneling Spectroscopy The use of STS to probe the occupied and unoccupied electronic states and par-

28

Nanoscale Characterization of Surfaces and Interfaces I

I

I

106 105 104 103

102 10 1 01

-

f ,3

g

-

I AS

0

Figure 23. (a) Expeimental geometry and potential energy diagram for calculations of standing wave oscillations in the tunneling gap. (b) Measurements of d l JdV and gap distance as a function of bias voltage compared to theoretical curves with (solid) and without (dashed) image potential contribution (Becker et al., 1985a). (b)

GAP BIAS VOLTAGE (v)

ticular sites on a surface involves elastic tunneling through the vacuum gap. Electrons passing through the vacuum tunnel gap may also be expected to produce vibrational or electronic excitations by a process analogous to inelastic electron tunneling spectroscopy (IETS). The localized flow of current from a tip has been

proposed as a means to probe individual adsorbates in their local bonding environments. The vibrational interaction has been considered theoretically in this context (Persson and Demuth, 1986; Persson and Baratoff, 1987; Baratoff and Persson, 1988). An inelastic loss would be observed as a change in slope of the differential con-


ductance at an energy referenced to the elastic signal. These types of measurements have the potential to provide the vibrational or electronic signatures of a segment of an adsorbed molecule just beneath the tip, even if it is “invisible” to imaging at a particular bias. In surface chemistry this could provide information on reactions at active sites on a surface which may reside at or near steps or defects. The theoretical treatment of inelastic tunneling for vibrational excitations can be derived from the formalism similar to that used for electron energy loss spectroscopy (EELS) (Ibach and Mills, 1982), where the inelastic signal intensity is typically < 1% of the elastic background. Inelastic tunneling demands a high signal-to-noise ratio for spectroscopy. For chemisorbed species on metals, model calculations (Persson and Baratoff, 1987) predicted that adsorbateinduced resonances in the vicinity of E , could increase the inelastic signal by a factor of 10. In addition, symmetry considerations must be included to determine the coupling of wavefunctions between tip and sample. Furthermore, when the current passing between the tip and the sample is compared to the vibrational relaxation time, it has been noted that many of the adsorbates will be probed in an excited vibrational state. Such demonstrations of inelastic tunneling with an STM have yet to be convincingly demonstrated. A variation of this concept allows the observation of plasmon modes included by the interaction of electrons emitted from the tip. Inelastic interactions of both tunneling electrons and field-emitted electrons on Ag surfaces have been shown to induce optical emission (Berndt et al., 1991) which, if plotted as a function of the scanned tip position, produces a map of the regions where the inelastic excitations originate.

-

29

2.2.4 Ballistic Electron Emission Microscopy (BEEM) Ballistic electron emission microscopy combines electron tunneling and ballistic electron transport through ultrathin metal films to image inhomogeneities at buried metal-semiconductor interfaces (Bell and Kaiser, 1988; Kaiser and Bell, 1988). As a spectroscopic technique, BEEM provides the capability to measure local Schottkybarrier heights (SBH) and the electronic structure of such interfaces. BEEM operates in a three-terminal configuration, as depicted in Fig. 24. Electrons tunneling from the tip are injected with a current I , into a thin ( - 100 A) metal layer (base) that is deposited on a semiconductor surface (collector).We consider a case in which the base is grounded and the tip is biased at V,. As the bias is swept, a threshold bias is reached when the collector current I , becomes non-zero, and this represents the local SBH. These electrons experience ballis-

_ _ _ _ _ _

.)/ ,/,’,

,. , I

,/’, ’

BASE

,

COLLECTOR

Figure 24. Three-terminal configuration of the BEEM experiment: (a) zero tunnel bias condition; (b) with a tunnel bias voltage above the barrier height (Kaiser and Bell, 1988).

30


tic transport, having traversed the thin metal layer without energy loss. By the simple theory, above the barrier threshold, the collector current varies linearly with V, when I, is the held fixed by feedback control of the tip-sample distance. In this mode, electronic states near the threshold and far above the threshold can also be characterized. It must be realized that, depending on the quality and thickness of the overlayer and the temperature of the system, electron -electron and electronphonon scattering effects must be taken into account. Since momentum and energy must be conserved at the ordered interface, the ballistic electrons are focused forwards providing a high degree of spatial resolution. Therefore regions of different barrier heights can be distinguished by scanning the tip at a bias above some nominal V,,, and measuring I,. Not only does such an image contain features due to SBH differences, but it may also contain geometric variations at the surface and at the interface. The surface topography can be handled by acquiring an STM image quasisimultaneously, but the interface structure is more difficult to characterize. The basic concept of BEEM can be described starting with free electron densities of states for the tip and the base, and considering a parabolic conduction band minimum (CBM) for the semiconductor. Electrons traversing the base with negligible scattering must conserve energy ( E ) and transverse momentum (k,)at the interface where structural order exists. Satisfying both conditions requires that electrons that enter the semiconductor traverse the metal base with a small angular deviation from the normal (with respect to the interface plane) since the range of transverse momenta is limited. A critical angle, 8,, with respect to the normal direction can be

defined as

where rn is the free electron mass and rn, is the electron effective mass parallel to the interface. The range of transverse momenta can be written in terms of a “transverse energy” El such that (1 5 )

where E x is the energy associated with the component of the electron wavevector normal to the interface. The small critical angle provides high spatial resolution. For example, a 100 8, Au layer on Si results in a critical angle of 4”so that scanning the tip (the injector) can provide a mapping of inhomogeneities in the barrier height at the interface with 10 A lateral resolution. The collector current can be written as

-

I c ( V )=RZ,CD(E,)F(E)dE,dE,

(16)

with Em,, = El and Emin= E , - e (V - vb), the minimum energy to overcome the Schottky-barrier (Vb is the base voltage). This yields a relation which is linear in injected current, I,, and scattering resistance, R, which is taken as an energyindependent scattering parameter. Just above the threshold, I , K (I/ - Vb)’, and I,K (V-Vb) for larger I/: The barrier height can be obtained by fitting the I , versus V data. Just as STS provides a means of measuring the surface electronic states, BEEM can be used to measure electronic states at the interface. Taking dI,/dV versus V,, deviations from the apparent linear dependence of I , versus V, become clear and can be interpreted in terms of the interfacial band


structure. The existence of multiple differential conductance thresholds implies that several conduction channels may exist at the metal-semiconductor interface. The first threshold is related to the barrier height and subsequent threshold values distinguish other aspects of the interface. More complete theoretical treatments of BEEM take into account several factors that affect the collector current (Ludeke et al., 1991; Ludeke, 1993). In particular, the electron mean free path in the base results in an attenuation factor that depends exponentially on the electron energy; the transmission probability across the interface depends on both the degree of momentum conservation across the interface, due to the interface roughness or lack of epitaxy, and a quantum mechanical transmission factor across an abrupt potential step. Quasi-elastic scattering in the base, primarily from electron-electron scattering, results in a broadening of the momentum distribution incident upon the interface. In addition, temperature-dependent broadening must be included when fitting to data. Modeling all these effects has been shown to lead to an I, cc (V - V0)5/2power dependence [rather than I, cc (V - V,)') yielding a superior fit to BEEM spectroscopic data on interfaces where such considerations are important.

2.3 Instrumentation The STM is a near-field imaging instrument operating on the principle of electron tunneling between an atomically-sharp probe tip and a sample surface. Images are obtained in the constant current or constant height modes by scanning the tip laterally over the surface while tunneling. The tunneling current, I,, exhibits a nearly exponential dependence on the tip-sample separation, s; the tunneling probability is

31

proportional to e-2as, where a - 1 A-' for a barrier height of 4 eV. I, is of the order of 1 nA for s x 10 A, and is reduced by a factor of 10 for every 1 8, change in separation. Maintaining a stable tunnel junction with an accuracy of 0.01 A, as the tip is scanned over the surface, is the most crucial aspect of STM operation and therefore demands that the apparatus exhibit high mechanical stability. In addition, since the tip and sample are typically mounted at points much further apart than the tipsample separation, thermal drift must be compensated for and a high degree of vibrationlshock isolation must be ensured. The STM head is typically designed to meet the criteria of the measurements which are to be performed, e.g. constant temperature versus variable temperature, atomic resolution versus wide scan range. The first step to meet these goals is to design a rigid structure in the STM head keeping uniformity of thermal expansion coefficients in the materials used. This provides the apparatus with a high resonance frequency, aiding in isolating vibrations from the surroundings; uniform materials provide good thermal drift characteristics. Obviously, tip structure and preparation is important to obtain atomic resolution images, and several methods have been developed and tested. One of the key technical problems in operating an STM is the coarse approach allowing the tip- sample separation to proceed from macroscopic distances to the tunneling regime. This aspect largely dictates the microscope design, being handled successfully in a number of ways - mechanically or electro-mechanically. Microactuation of the probe tip is usually accomplished using piezoelectric transducers for motion in each of the three orthogonal directions. With low-noise drive circuitry, electrical control can approach 50.01A. The electronics incorpo-

-

-

-

32


rate low-noise current preamplification, and, in the constant current mode, tunnel current feedback controls the height of the tip by adjusting the z-piezoelectric element as the tip is rastered in the (x,y)-plane. Scanning the tip, setting or scanning the tip-sample bias, and other data acquisition tasks are performed in real-time by a microcomputer, while image analysis and processing can be performed by the same microcomputer or off-loaded to workstations or mainframes. In this section, these basic elements of STM system design, as illustrated schematically in Fig. 25, are discussed.

2.3.1 Microscope Design: STM Heads Positioning the sample in the tunneling regime typically begins several centimeters away using some coarse approach method. Once in the tunneling range,fine motion is typically accomplished by piezoelectric actuators. For various microscope designs, coarse approach has been performeid by mechanical or non-mechanical methods, typically moving the sample towards the tip fixed on the piezoelectric actuator. If a purely mechanical coarse approach system is employed, the mechanical connection to

the outside world must be decoupled from the microscope while scanning; the coarse advance steps must be small enough to accommodate the maximum extension of the z-piezo. Coarse approach can be accomplished electromechanically with a louse, as discussed previously, with piezoelectricbased slip-stick inertial mechanisms, or using piezoelectric inchworms. The fine motion is used for final approach and scanning the tip during measurements. Several methods are illustrated in Fig. 26. Tip scanning was initially done using piezoelectric tripods, where elongation of each element provided x, y, z motion (Binnig et al., 1982a; Demuth et al., 1986; Sakurai et al., 1990). Soon thereafter, segmented tubular piezoelectric elements utilizing elongation for z motion and bending for x,y motion (Binnig and Smith, 1986; Lyding et al., 1988; Snyder and de Lozanne, 1988),bimorph-driven tripods (Blackford et al., 1987), or microfabricated bimorphs (Akamine et al., 1989) were introduced. Smaller and lighter elements increase the resonance frequency of the elements while reducing the effects of thermal gradients. Cross-talk between orthogonal motions are minimal for scanning ranges that extend up to the micron scale. SensiFigure 25. Schematic diagram indicating the major components of an STM system. An atomically-sharp tip is biased with respect to the sample. In the constant current mode, the three-dimensional piezoelectric scanner assembly is scanned over the surface by the computer which controls the x-piezo and y-piezo biases. As the tip is scanned, the amplified tunneling current is compared to a reference signal, and the result is fed back as an error signal to control the bias on the z-piezo. The error signal also provides the height signal to the computer to form the image shown on the display monitor (Kuk and Silverman, 1989).


33

(a) PIEZ 0( PZT 1 Z-AXIS

..4 . I

ELECTROSTRICTIVE Z-AXIS(C0ARSE)

(b) PIEZOELECTRIC

X - o c ELECTRODE

'X-dc

Figure 26. (a) A piezoelectric tripod provides three-dimensional fine positioning of the tip while an electrostrictive element allows coarse approach (Sakurai et al., 1990). (b) A quartered tubular piezoelectric element provides, x, y , and z motion; in this case the tip is mounted off-axis (Binnig and Smith, 1986). (c) Bimorph-elements (hidden in block) mounted on the main support block drive the tripod frame (Blackford et al., 1987). (d) A microfabricated piezoelectric actuator permits lengthwise, lateral bending, vertical bending, and twist motions (Akamine et al., 1989).

tivities of the order of tens of angstroms per volt make motion in steps of 0.1 8, in the xor y-direction easily controlled by independent operational amplifiers each connected to a digital-to-analog converter for raster scanning by the data acquisition microcomputer. We noted in the introduction the elaborate set-up for the first STM from Binnig and Rohrer using magnetic levitation, a louse, and a tripod assembly (Binnig et al., 1982b, 1983b). In this section, several other designs are discussed to illustrate the conceptual variations in design and the evolution of the instrumentation. The UHV-STM design of Sakurai et al. (Sakurai et al., 1990),shown in Fig. 27, was modeled on the Demuth design (Demuth et al., 1986). The sample is mounted on a double-hinged flip mechanism so that the sample approaches the tip from a vertical position rapidly until (right) the sample arm swings down (on pivot A) and rests on the stopper (foot) located near the tip and slightly protruding. The swing arm allows the sample to be accessed by other surface probes such as low-energy electron diffraction (LEED) and Auger electron spectros-

34


Figure 27. The UHV-STM with a double-hinged sample approach allows sample approach with hinge A and fine mechanical approach with hinge B (Sakurai et al., 1990).

MIC R 0METER

copy (AES), and the tip can be viewed by a moveable field ion microscope. Once the sample rests on the stopper, two coarse-approach philosophies are employed. First, exploiting the mechanical advantage between the second pivot (B) and the stopper (- 40:1), a fine-thread screw tilts the sample arm to bring the sample into the tunneling range. Secondly, with the feedback activated, the tip can be extended by the electrostriction actuator (motion 12 pm) as well as by the z-piezoactuator until a tunnel current is sensed. Once tunneling is achieved, the mechanical drive is decoupled for vibration isolation, the electrostriction actuator is held fixed, and the fine control takes over operation of the tip. One of the first designs for imaging and spectroscopy at low temperatures is shown in Fig. 28 (Fein et al., 1987).Used for appli- . cations in superconducting materials, low temperatures are obtained by insertion into a research liquid helium dewar and the unit is surrounded by a superconducting magnet, so the design must be compact. In this design, materials were chosen to minimize differential expansion or contraction to obtain a satisfactory coarse approach without tip crashes as the unit

is cycled between room temperature and liquid helium temperature; molybdenum was used for the majority of parts for its low coefficient of thermal expansion. The coarse approach is performed before the

MAGNET WINDINGS

-

1

COARSE AOJUST

0 0

SCREW

Figure 28. STM designed for use in a liquid helium dewar in high magnetic fields incorporating mechanical coarse approach and a tube scanner (Fein et al., 1987).


sample is introduced into the dewar by simply deflecting the cantilever sample mount. The fine approach is done mechanically by distorting the thin plate on which the tubular piezo is mounted using a finepitch screw which pushes on a soft spring in contact with the plate. This “differential spring” produces a mechanical advantage of 1OO:l giving suficient sensitivity to enter into the tunneling regime. This microscope uses a segmented (quartered) tubular piezoelectric element introduced by Binnig to replace the tripod as a compact element with a significantly higher resonance frequency (as high as 100 kHz) (Binnig and Smith, 1986). The inner surface of the tube is usually kept at a uniform potential and independent potentials are applied to each of the four outer quadrants. Operating in a bipolar configuration, opposite polarities are applied to opposite quarters to provide parallel motion, as illustrated in Figure 26b. The electromechanical properties for bipolar operation of the tubular piezo are based on the piezoelectric coefficient, d , , , and geometric analysis (Chen, 1992). The z-motion is obtained by establishing a uniform potential difference, AK between the inner and outer electrodes, i.e., AVL AZ = d 3 , =K, AV h where L is the length of the element, h is the wall thickness of the tube, and K is the piezo constant. Lateral motion of the tip is accomplished by applying opposite voltages on opposed quarters, so that one side of the element contracts and the other expands creating positive and negative stresses parallel to the tube which translate into strain perpendicular to the tube axis. Analysis of this situation leads to AVL2 Ax=Z,,hd,, = K I 1AV (18) nDh

-

-

~

~

35

where D is the diameter of the element. The expression for A y is identical. In practice, three-dimensional motion of the tip is obtained by modulating the center contact with respect to the potentials on the quadrant to obtain z-motion of the tip while the quadrants are modulated with bipolar x and y potentials, for raster scanning. For a PZT-5 H element, where d , , = 2.74 &V, and with D = 1.27 cm, h = 0.102 cm, and L = 1.27 cm, K, x 34.1 8,/V and K x 30.7 W/V. In order to maintain control to < 0.1 8,, noise in the driving voltages must be kept below 3 mV. With the proper piezoelectric materials and dimensions and increased voltages, scanning ranges up to tens of microns can be achieved. Intermediate translators may be used to scan widely-spaced regions on large-area samples (Hipps et al., 1990). The microscope design shown in Fig. 29 uses coaxial tubular piezoelectric elements, employs a coarse slip-stick inertial approach, and exhibits excellent temperature compensation resulting from a single mounting point for the coaxial tubes (Lyding et al., 1988). The outer tube, on which the sample support is mounted, is used as a sample approach by providing a series of pulse sequences involving pulsed outward motions, where the sample remains stationary as the force of static friction is exceeded, and slow inward motions pull the sample nearer the tip. The sample is removed using the opposite sequence of pulses. Adjusting the magnitude and timing of the pulses can vary each step length from 5 8, to 1 pm, and the speed of approach up to 1 mm/s. The inner quartered tube operates in the same fashion as the instrument described previously. In the original design the microscope was housed in a temperature control shroud, which provided an ability to heat or cool with the microscope maintained at a fairly uniform

-

--

36

Nanoscale Characterization of Surfaces and Interfaces Canpensation and Translation Tube

ChroM Healer Mnding

Tunnelihg Probe Details

temperature. As previously noted, the variable temperature capability of this microscope is enhanced by the fact that both tubes, being constructed of similar equal materials, expand and contract at the same rate with respect to their common mounting point. The STM illustrated in Fig. 30 (Frohn et al., 1989) has been operated in ultrahigh vacuum (UHV) at variable temperatures down to -20K. The high thermal conduction to the sample is made possible by

,

MICROSCOPE DISC

,SUPPORT RING

SUPPORT

--T i .-+

PIEZOCERAMIC T u t x

SAMPLE

SAMPLE RING

4 HM I \

2

E x

Figure 30.STM using a novel coarse approach philosophy in which three piezoelectric support legs are inertially-driven to rotate the microscope disc down three ramps on the sample ring (Frohn et al., 1989).

Figure 29. STM designed with inertial coarse approach and coaxial piezoelectric tubes for temperature-compensation. The STM is operated in a thermal shroud (Lyding et al., 1988).

its direct attachment to a liquid He dewar. This microscope design concept is based on a compact design using a novel approach mechanism (Besocke, 1987). The tip holder and three piezoelectric legs are mounted as a unit which rests on a triplygraded ring that surrounded the sample. The tip unit is set on the ring from above and is decoupled from the manipulator. Applying pulses on the three legs in a tangential direction allows the tip unit to rotate and descend down the grades until the tunneling regime is reached. At that point lateral movement of the legs can be used for x-y scanning. The sample can be heated or cooled by attachment to a heat source or sink, while the small size and low thermal conductivity of the tip assembly keeps thermal gradients within the microscope to a minimum (Wolf et al., 1991). High-temperature STM operation is especially problematic due to thermal drift, as well as due to the relatively low Curie temperature of the piezoelectric elements. A recently introduced high-temperature UHV STM (Watanabe et al., 1990) utilizes direct sample heating and exhibits excel-


lent thermal isolation of the piezoelectric elements from the heater. This is accomplished by mounting a small sample on a pyrolytic BN insulating film on top of a graphite heater. The anisotropic thermal conductivity of BN ensures a uniform temperature distribution, and the direct resistance heating requires only small wires to attain temperatures up to >400°C.The sample is mounted on an inchworm for coarse positioning. The tip is mounted on a block which is driven by four Invar arms each attached to a bimorph piezoelectric disc. The piezoelectric elements remain near room temperature for the entire range of sample temperatures so that they maintain a constant sensitivity. Furthermore, the symmetric arrangement of drive arms compensates for thermal drift effects.

37

Construction of a microfabricated STM of sub-millimeter dimensions has been demonstrated using planar processing techniques (Akamine et al., 1989), as illustrated in Fig. 31. Besides opening up new applications in lithography, data storage, or sensor technology, the small size reduces the magnitude of thermal drifts, increases mechanical resonance frequencies, and reduces sensitivity to external vibrations. In this design, the cantilever of dimensions 1000 x 200 x 8 pm was constructed from alternating layers of metal electrodes, dielectric films, and well-oriented piezoelectric ZnO films on an Si substrate to provide full three-dimensional motion. Tips were formed at the end by metal evaporation or attachment of metal wires or particles.

Figure 31. Design of a microfabricated STM using a piezoelectric bimorph cantilever (section) for three-dimensional motion (Akamine et al., 1989).

38


2.3.2 Tips Theory suggests that the lateral resolution that can be obtained by an STM is directly related to the atomic sharpness of the tip. The corrugation amplitude, A , is given by the relation A e-B(R + 4 (1 9)

-

where /? x- C2/4, with x the inverse decay length, G the smallest surface reciprocal lattice wavevector (directly related to the corrugation width), d the gap distance, and R the radius of curvature of the tip (Kuk and Silverman, 1986). That tips can be prepared with one or a few atoms protruding and the fact that the tunneling probability decays rapidly with separation permits atomic resolution to be achieved more or less routinely, although multiple protrusions in approximately the same plane can produce anomalous images. Several materials have been used successfully, with specific methods of tip preparation having been developed for each material, ranging from mechanical extrusion and/or grinding (e.g., PtIr tips) to electrochemical etching (e.g., W tips). In addition, microtips of sub-micron dimensions have been fabricated by e-beam deposition to obtain a high aspect ratio for the study of deep structures (Akama et al., 1989). It must be noted that the material at the surface of the tip is important since spectroscopy depends on the joint density of states between the tip and the sample. Examination of the tip by electron microscopy gives a general measure of shape and sharpness, but not an atomic scale view. Atomically-resolved STM images are generally obtained after in situ preparation using high-biases (field-evaporation or atom transfer/rearrangement) or high currents (tip annealing), but care must be taken not to blunt the tip by such processing.

While typically routine methods are followed to fabricate tips that operate satisfactorily, one pioneering study established a connection between the tip atomic structure of W, as obtained by field ion microscopy (FIM), and STM imaging resolution (Kuk and Silverman, 1986). Tungsten is a tip material which has received widespread use, partly because the surface energy of the (110) facets of b.c.c. metals can be formed by annealing in a high electric field. Using electrochemically-etched single-crystal W (1 00)wire and in-situ field-evaporation, a tip with six atoms protruding as a distorted p ( 2 x 2) reconstructed W(100) surface was characterized prior to and after imaging the Au(001)-(5x 1)reconstruction, as shown in Fig. 32. The measured STM imaging resolution of - 4 A is in agreement with theory. Smaller tip clusters were found to be unstable, although they are absolutely essential for imaging closepacked metal surfaces. The sharpness of the W tip was severely reduced, as was the measured corrugation of the Au surface using such a tip after cleaning using field evaporation. It should also be noted that spin-polarized imaging on the nanometer scale has been demonstrated using ferromagnetic CrO, tips is study Cr(001) (Wiesendanger et al., 1990) and ferromagnetic Fe tips to study magnetite (Fe304) (Wiesendanger et al., 1992).

Figure 32. The FIM image of a tip grown on a singlecrystal tungsten wire on the right is interpreted as originating from the arrangement of six tungsten atoms (left) in a b.c.c. (110)-like structure (Kuk and Silverman, 1986).

2 Scanning Tunneling Microscopy

n:

STM ASSEMBLY

2.3.3 Vibration and Shock Isolation The first STM was levitated on a superconducting magnet system (Binnig et al., 1982b). This extremely effective vibration isolation system demonstrated and developed the true potential of the technique (Binnig and Rohrer, 1987), permitting Binnig and Rohrer to concentrate on understanding the tunneling mechanisms and spatial resolution of the instrument. All of these unknown aspects combined to prevent previous researchers from achieving vacuum tunneling, but vibrational isolation was the most serious. With better understanding of the tunneling mechanism and the experimental constraints, relaxing the sophistication of the vibration isolation system and refining simpler designs has led to the proliferation of STMs of both custom and commercial types. Isolation of the STM from vibration and shock from the external environment is critical for its operation. Once the STM head design has been selected, the vibration isolation system to operate in the ambient environment can take several forms. The elements of a vibration isolation system are depicted in Fig. 33. The principal consideration in planning the vibration isolation system is the high sensitivity of the current to tunneling distance (AIII per angstrom is -10) and the magnitude of topographic variations in the z-direction ( - 0.1 8, or less). The goal is to limit the vibration amplitude between the tip and the sample to 50.01 A. Typical sources of vibration are from the building floor ( < 5 Hz); from electromechanical devices, ventilation systems, and transformers (typically < 120 Hz, with particular activity in muItiples/sub-multiples of the line frequency); and from acoustic noise. The STM can be isolated from high frequency vibration (> 1 kHz) by a factor of lo6

-

mx

I

Yn

Y

1

ISOLATION TABLE

Figure 33. Block diagram showing parameters for the modeling of vibrational isolation for a typical STM (Kuk and Silverman, 1989).

using spring suspensions or elastomer supports. Fabricating the STM as a rigid structure with a resonance frequency in the high kHz range is the first step in decoupling the tunneling gap from low frequency vibrations. However, the suspension systems themselves exhibit low frequency resonances; their amplitudes can be reduced (while also increasing the slope of the highfrequency roll-off) by the use of multiple suspension stages and by mounting the entire apparatus on pneumatic supports. Disturbances due to shock can be removed by incorporating damping in the vibration isolation system. A practical anti-vibration system consists of an STM chamber suspended on pneumatic legs or hanging from a spring suspension. The STM is itself structurally rigid, and it rests in the vacuum system on a series of stacked plates separated by elastomer spacers (Gerber et al., 1986). Recent calculations have found that optimum performance can be obtained by using a few stacked plates for STM mounting with soft suspension of the entire chamber (Schmid

40

B


chamber

100

8.9 Nslm

60 kNlm

10-2

10-4

10.6

El chamber

10-8 100 kN1m 500 kg

0.1

1

10

100

Figure 34. Amplitude transfer functions for: (a) chamber supported by a pneumatic suspension system; (b) chamber supported by a spring (with damping); (c) STM supported on a threestage stack in a pneumatically supported chamber (not illustrated); (d) tipsample distance of STM with resonance frequency of 3 kHz (Schmid and Varga, 1992).

-

1000

frequency [Hz]

and Varga, 1992). Figure 34 depicts amplitude transfer functions for a chamber supported by (a) a pneumatic suspension system or (b) a spring suspension system with damping and incorporating realistic values of spring constants and damping coefficients. It is seen that the spring suspension has a higher frequency but higher amplitude resonance with a steeper high frequency roll-off than the pneumatic system. However, the pneumatic system is more practical. When the STM is supported on a three-stage stack (c) in a chamber suspended by pneumatic legs, the high-frequency roll-off is greatly enhanced. Furthermore, if the STM with resonance is at 3 kHz, the reduction in coupling to the tunneling gap over the entire frequency range is approximately six order of magnitude or better, as shown in curve (d). An alternative method of damping involves suspending the STM from coil springs and using an eddy-current damping system, as depicted in Fig. 35 (Okano et al., 1987). This two-stage caged system involves hanging a middle frame (11) from the base frame (I), which may be the chamber possibly sitting on a pneumatic suspension, by three springs. The exterior frame

-

(111) is likewise supported by three springs attached to 11. Each coil spring end is terminated by an elastomer ring. One eddy current damper is shown; it consists of copper blocks (IV) and (VI) surrounding a permanent magnet. These dampers attenuate vertical and rotational motion of the suspension. The transfer function for this suspension system, calculated and then compared experimentally using a vibration transducer and an acceleration sensor, is shown in Fig. 35 B. Without damping, there are two main resonances at 2 Hz and 5 Hz and an acoustic noise peak at 50 Hz. The inset shows the vibration of the set-up as a result of mechanical shock. Introducing damping suppresses all the vibrational features, and shocks are rapidly damped.

--

-

2.3.4 Electronics

Figure 36 depicts a typical schematic diagram of analog control electronics for STM operation. Note that in this diagram (Kuk and Silverman, 1989) there are two z-piezoactuators - one microcomputercontrolled and one feedback-controlled. Scanning is accomplished by microcom-


I

1

U

m

v

m

(8)s2 0 y 1

1

I

I

1

v

I

1

I

1

WITHOUT DAMPER

5

0 (a)

10

20

I

I

30

I

I

40

I

50

FREOUENCY (Hz I

g-50 a

(b)

FREOUENCY ( Hz 1

Figure 35. (A) STM suspended by coil springs with eddy-current damping in a two-stage caged system. The calculated transfer function is compared with experiment (B): (a) without damping; (b) with damping. The oscilloscope traces show the response of the suspension system to externally-applied shock (Okano et al., 1987).

41

puter-controlled digital-to-analog converters (DACs)operating high voltage preamps connected to the x (DAC2) and y (DAC3) piezoactuators while the z piezoactuator (DAC4) sets a coarse z-position. For single-tube piezo scanners operated in the bipolar mode, the z-bias is connected to the inner cylinder while the i-V, and k V, are applied to opposite quarters of the outer type. The tip is biased by a variable voltage which is also microcomputer-controlled (DAC1); it is important that the tip be shielded from both leakage currents and capacitive coupling to the modulated piezo biases. The tunneling current is monitored through the sample, which is connected to a current preamplifier. Information passes to the microcomputer through analog-todigital converters (ADCs). Three modes of operation can be distinguished - constant height, constant current and spectroscopic. In the constant height mode, the tip-sample distance is set and the tip is scanned while the microcomputer acquires tunneling current as a function of position through the current ADC. In the constant current mode, the preamplifier signal is passed through a logarithmic amplifier to linearize tunnel current and tipsample separation (i.e., log I cc s) and this signal is compared with a voltage related to the desired tunneling current (demanding current or reference current) using a comparator. The error signal generated by the feedback circuit is processed through both a proportional amplifier and an integrating amplifier and then passed through a high-voltage amplifier to correct the tip position to obtain the desired tunneling current. This error signal is likewise read by the microcomputer (tip position, ADC) and is directly translated to the height. Analog feedback has often been used in STM control systems, but digital feedback has recently been introduced in several in-

42

Nanoscale Characterization of Surfaces and Interfaces r

DAC -

T I P PnCllTlON ADC

1

COMPUTER

--CURRENT

Figure 36. Schematic diagram of STM control electronics illustrating circuits for constant-current, constant-height, or spectroscopic modes (Kuk and Silverman, 1989).

STM TIP DRIVER

DEMANDING CURHENT

struments. In studying the details of the feedback system, including the electronics and piezoactuators, the response of the scanners introduces an inherent time delay in the circuit that must be addressed. In practice, the feedback loop is operated with the maximum response which does not cause the system to oscillate; variable RC filtering, which introduces an additional phase shift, is used to prevent instabilities due to sudden changes in tip current due to irregularities in the surface or externally-introduced shock. Operating with too high a time constant limits the feedback response, resulting in unacceptable smoothing of the surface image. Several spectroscopic modes exist that utilize a sample- hold to open the feedback loop during I- I/ measurements. While sampling, the height is set at a desired tipsample bias and tunneling current; then, while the height is held fixed, the bias is scanned and the current versus bias is recorded through the current ADC. Thus an image and a spectrum are obtained for various positions.

Combining lock-in techniques with the STM electronics can significantly reduce noise (Abraham et al., 1988), and such techniques are commonly used in non-contact AFM systems, as will be discussed in the next section. Briefly, a dither voltage is placed on the z-piezo to oscillate the tip in and out at a specific frequency. The lock-in synchronously detects the signal, reducing contributions from unwanted noise with frequency components spanning the rest of the spectrum. Progressively increasing speeds in communication between microcomputers and instrumentation have allowed the introduction of real-time digital feedback and digital signal processing for STM applications. Digital feedback control is advantageous since it permits a complex signal processing algorithm to be implemented in the software. For example, one such system contains two software control modules (Morgan and Stupian, 1991). One module emulates the logarithmic amplifier using a look-up table to linearize the tip-sample distance versus the current relation. The


second module is a proportional-integraldifferential controller, which allows the gain and the feedback loop parameters to be adjusted during a scan to achieve optimum operation, depending on tip and surface conditions. 2.3.5 Microcomputer Control

Figure 37 shows a microcomputerbased STM workstation for data acquisition and image processing. Control is implemented by a microcomputer and software operating DACs, ADCs, and video peripherals and driving various image analysis and spectral analysis routines. Typically, all control functions are controlled from the keyboard, and images are displayed during acquisition. After acquisition, several functions are generally available to noise-filter, analyze, and portray data in the form of topographic and spectroscopic images and atomically resolved spectra. 2.4 Semiconductor Surfaces 2.4.1 Si(ll1)

Si(lll)-7x 7 - Atom-Scale Topography and Spectroscopy The use of STM to solve the geometric structure (Binnig et al., 1983) and the electronic structure (Hamers et al., 1986) of the

43

Si(ll1)-(7 x 7) reconstruction has briefly been discussed in Sect. 2.2. Such work added crucial detail to support the dimeradatom-stacking-fault (DAS) model proposed independently, based on an electron microscopy analysis (Takayanagi et al., 1985). Total energy calculations further supporting the DAS model have recently been reported (Brommer et al., 1992; Stich et al., 1992). Other Si(11 1) structures exist, most notably the (2 x 1) which represents a doubly periodic superstructure in one direction, while the (7 x 7), the stable reconstructed phase, is sevenfold-periodic along both principle axes spanning 49 surface unit cells. In addition, (5 x 5) and (9 x 9) reconstructions have been observed (Becker et al., 1986; Becker et al., 1989; Feenstra and Lutz, 1990; Feenstra and Lutz, 1991 a). The first in vacuo experiment of Binnig and Rohrer unambiguously showed that the (7 x 7) structure comprises an array of 12 Si adatoms, which were found to be arranged locally in a 2 x 2 structure, nine dimers on the sides of triangular subunits of the 7 x 7 unit cell, and a stacking fault layer (Takayanagi et al., 1985). These STM topographic images, shown in Fig. 12 a, are line scans recorded on a chart recorder with v = 2 . 9 V . The measured rhombohedra1 unit cell diagonals of 46 x 29 8, bounded by deep corner holes

Microcomputer Shear-mode

1 Mouse circuit

Bias circuit DC source

Figure 37. Microcomputer-based STM workstation with video accessories as peripherals (Iwatsuki and Kitamura, 1990).

44


encompass twelve maxima. Since tunneling mainly involves dangling bonds protruding into the vacuum, a model incorporating twelve adatoms was supported. That is, the twelve maxima are from threefold-coordinated Si adatoms with empty sites at the corners (corner holes). The “rest atoms”, atoms in the next layer with unsatisfied dangling bonds, were not imaged at this bias. In addition to verifying an adatom model, a displacement of the adatom structure with respect to the underlying surface by 2 %, for half of the unit cell was observed for positive sample bias (unoccupied states) due to the stacking fault. Further details of the reconstruction were explained by subsequent studies using spectroscopic imaging (Becker et al., 1985b) and CITS (Hamers et al., 1986~). As noted in Sect. 2.2, such studies represented the first demonstration of the need for combined spectroscopic and topographic imaging as a means to explain STM images. Figure 21 presented CITS images at three bias voltages mapping occupied states. A more complete set of CITS images is displayed in Fig. 38, showing that the adatoms have both occupied and unoccupied character ( - 0.35 eV and 0.50 eV). The 0.35 eV state gives rise to the faulted/unfaulted asymmetry typically observed in unoccupied state images. Another unoccupied state appears between the adatoms with different onset energies for the faulted and unfaulted halves.

-

Si(lll)-2x 1 - Structure, Spectroscopy, and Local Defect Structure An analysis of the Si(ll1)-2 x 1 reconstruction on cleaved Si(l11) samples (Feenstra et al., 1986) supported the proposed n-bonded chain structural model (Pandey, 1981; Pandey, 1982)of this reconstruction. In the 2 x 1 reconstruction, occu-

A

H

C

D

K

E

L

F

M

G

N

Figure 38. CITS images of the Si (1 11)-7 x 7 surface with the feedback loop at V, = - 2 V. Images are shown at the following biases: (A) +0.15 V, (B) +0.25 V, (C) +0.65 V, (D) +0.75 V, (E) +0.95 V, (F) +l.55V, (G) +2.0V, (H) -O.lSV, (I) -0.25V, (J) -0.65 V, (K) -0.75 V, (L) -0.95 V, (M) -1.55 V, (N) -2.0 V (Hamers et al., 1986b).

pied and unoccupied surface states around the surface Brillouin zone (SBZ) boundary are separated by 0.4 eV, while states at the SBZ center mix with the bulk bands. The existence of states within the gap provided the contrast for surface images of the n-bonded chains shown in Fig. 39. Long atomic rows along [Oli], separated are observed to coexist with disby 6.9 %,, ordered regions where the rows merge and hillocks are observed. This spacing is consistent with delocalized n-derived bands

-


45

C)

Figure 39. (A) STM image of cleaved Si(ll1) surface acquired with V, = -0.6 V. 2 x 1 n-bonded chains are observed on the left side and a disordered region is seen on the right side. (B) Expected corrugation for tunneling into and out of surface states of the (a) buckled model and (b) n-bonded chain with experimental results (c) that indicate sample biases switched to +0.8 V (+) and to -0.8 V (-) on successive scans (Feenstra et al., 1986).

along the chains. Line scans across the chains produced a measured corrugation amplitude of 0.54 8, and the in-phase corrugation for both polarities is also consistent with the n;-bonded chain model. Subsequent spectroscopic measurements of the 2 x 1 surface were performed (Stroscio et al., 1986). The surface states with maxima at the zone-center (k0.2 eV) and at the zone edge (k1.2 eV) were observed in (dI/dV)/(I/V) spectra obtained at various heights above the surface chains. Differences in the electronic structure due to structural defects were also observed (Feenstra et al., 1986). For biases below those used to image the ordered 2 x 1 structure, the hillocks were clearly imaged, indicating disorder-induced modification of the electronic structure; these observa-

2

r\

tions supported results of EELS measurements of the 2 x 1 surface band gap (DiNardo et al., 1985).

Phase Transitions Between Si ( 1 1 1 ) Structures The kinetics of phase transitions between ordered reconstructions on Si(l11) up to the high temperature (1 x 1) structure have been obtained by temperature-dependent STM (Feenstra and Lutz, 1991 a; Kitamura et al., 1991; Miki et al., 1992; Hibin0 et al., 1993). Similar measurements on Ge(ll1) have also been reported (Feenstra et al., 1991). In an analysis of the time- and temperature-dependence of the (2 x 1) =+-(5 x 5), (7 x 7) reconstructions on an STM de-

46


signed to operate at temperatures up to -400°C (Feenstra and Lutz, 1991a), it was found that the process is temporally nonlinear for T I330 “C.This is due to the fact that the transition is dominated by the number of surface adatoms available; at 320”C, only an initial conversion to an adatom-covered 1 x 1 surface is required to make the adatoms available (another source of adatoms at low temperatures is at 2 x 1 domain boundaries). At 330”C, the surface orders into the ( 5 x 5 ) and (7 x 7) by creating DAS structures, thereby liberating more atoms for further growth, as shown in Fig. 40. In this image, monolayer-deep “holes” also appear; these are additional sources of adatoms. Above 330”C, (5 x 5) structures predominate with some (7 x 7) structures, forming without the adatom-covered 1 x 1 intermediate. Ordered 5 x 5 “fingers” extending along the [OlT] direction and nucleating around domain boundaries of the original (2 x 1) coexist with monolayer-deep “holes”. Here

-

-

-

the kinetics make it possible to form the structures so long as the number of atoms is conserved. In particular, the (7 x 7) is not favored because of a deficiency of adatoms; the 2 x 1 and 5 x 5 contain the same number of atoms while the 7 x 7 contains 4% more atoms. The formation of the ( 7 x 7 ) from the high-temperature (1 x 1) has been imaged with a new UHV microscope capable of stable operation above 900°C (Iwatsuki and Kitamura, 1990). Figure 41 begins with a current image acquired at 880°C. Due to the response of the feedback mechanism to avoid tip crashes at steps, steps bands appear dark if the left-hand terrace is higher than the right-hand terrace and appear light in the opposite circumstance. Lowering the temperature to 860°C results in completion of the (7 x 7) on the upper side of the step. The atoms appear to be in motion near the lower side of the step because the step itself is still in motion. At 840”C, the entire surface is covered with the (7 x 7) and the step is aligned along the direction of the (7 x 7) unit cell, along [Oli]. Time-resolved images of the (7 x 7) (1 x 1) transition obtained at constant temperature, acquired approximately every 17 s (Miki et al., 1992) in this range of temperatures, indicate nucleation of the (7 x 7 ) from step edges with fluctuations in the domain boundaries reduced as the temperature is lowered. The [Ti21 steps straighten as the (7 x 7) domain forms, because the unfaulted half of the unit cell is lower in energy that the faulted half. This leads to an equilateral triangular shape to the (7 x 7) domains bounded by unfaulted triangles. On vicinal Si(1 1 1) surfaces misoriented to [1 121, slender (1 11) facets containing a few (7 x 7) unit cells nucleate; these widen in quanta of the (7 x 7) unit cell width as the temperature is lowered (Hibino et al.,

-

Figure 40. STM image of the Si(ll1) surface annealed at 330°C for 900 s. (2 x l), (5 x 9, and (7 x 7) domains are seen with monolayer-deep holes containing (5 x 5) and (7 x 7) structures (Feenstra and Lutz, 1991 a).


47

Figure 41. STM images of an annealed Si(ll1) surface showing the formation of the (7 x 7) from the high-temperature (1 x 1) structure. (a) 100 nm x 100 nrn constant current image acquired at 880°C; (b)-(d) current images acquired at 880°C (50 nm x 50 nm), 860°C (100 nm x 100 nm), and 840°C (100 nm x 100 nm), respectively (Kitamura et al., 1991).

1993). These are separated by step bunches, which below 700 "C are transformed into (12 x 1) reconstructed (331) facets that coexist with the (111) facets which now contain both ( 5 x 5 ) and (7 x 7) structures. The ( 5 x 5 ) is more stable under compressive stress which might occur due to the presence of the steps. 2.4.2 Si(100)

Si(100)-2xI

The Si(100)surface is the technologically-important Si substrate material for microelectronics device fabrication. On a flat surface, locally-ordered 2 x 1 domains exist separated by monoatomic steps which produce a 90" rotation between them. Thus diffraction techniques such as LEED average over both domains. In addition, averaging techniques are less sensitive to the lack of atomic-scale structural homogeneity that may exist to a large degree, depending on surface preparation. Vicinal surfaces provide a means to obtain a dom-

inance of one orientation and, varying the miscut angle and off-axis direction, is a means to study terrace-step structures (Wierenga et al., 1987) and analyze kinkstep energetics (Swartzentruber et al., 1990). In the late 1970s, theoretical calculations and experimental observations of the electronic structure deduced that the reconstruction consisted of an ordered arrangement of Si surface dimers, which form to reduce the number of dangling bonds (Chadi, 1979).A further lowering of energy was predicted if an ordered (tilted) array of asymmetric dimers form since symmetric dimers should be unstable with respect to a Peierls distortion. This would render the surface non-metallic, as observed by STS (Hamers et al., 1986b) and other spectroscopies. The first STM images of this surface (Hamers et al., 1986b) directly confirmed that dimers are the basic building blocks of the reconstruction, as seen in Fig. 42. Biasdependent images showed that the occu-

48

1%


’ ? 12\

13

\

14 \

9\

5, 4,

3\

Figure 42. Occupied state topographic image of Si(OO1)-2x 1 (Hamers et al., 1986b).

pied state density is between the dimer atoms, while the unoccupied states are localized away from the dimer, as seen in Fig. 22. STM indicates that, in the absence of defects, symmetric dimers compose the terrace structures; near defects, however, a clear asymmetry is apparent. In Fig. 42, row 1 1 is a defect-free dimer row; several missing-dimer defects exist in other rows (e.g., row 9). Sometimes around such defects, the dimer rows appear as zigzag structures forming superstructures, which

suggests that a correlated tilting of the dimers occurs due to dimer-dimer interactions. At low temperature, LEED has provided evidence of higher-order structures with an order -disorder transition occurring at 220 K (Tabata et al., 1987). Ruling out tip-induced surface distortions (Huang and Allen, 1992), the negative observations of asymmetry in defect-free regions with room temperature STM led to the speculation that the dimers are oscillating between two tilted configurations and that, on the timescale of the STM measurement, these average to form a symmetric image (Hamers et al., 1986 b). Molecular dynamics simulations supported the picture of dimer oscillations within the time scale of the STM measurement (Gryko and Allen, 1992).At 300 K, the dimers switch between left-asymmetric / symmetric / right-asymmetric configurations and this switching is quenched at 200 K. A significant low temperature (120 K) STM study of the Si(100) surface confirmed this model (Wolkow, 1992). The image in Fig. 43 shows that an increased number of buckled-dimer domains occur on defect-free regions at 120 K. Some defects pin dimers into buckled configurations to inhibit good ordering due to strain effects. Explaining the low temperature observations requires adopting a double-well asymmetric potential, which further explains the non-metallic nature of this surface.

Figure 43. 200 8, x 200 8, image of Si(OO1) acquired at low temperature (120 K) with V, = 2 V. Domain boundaries are marked in the right panel (Wolkow, 1992).


49

Initial Stages of Epitaxial Growth Molecular beam epitaxy is an established method for obtaining atomicallyperfect semiconductor interfaces. Observing the initial stages of growth at the atomic level under various processing conditions provides a means to directly determine nucleation and growth processes. Homoepitaxial growth of Si on Si(OO1) was one of the first examples in which the growth kinetics were related to the ultimate equilibrium structures (Mo et al., 1989). Si deposition to sub-monolayer coverages was performed at sample temperatures between 300K and 500K. In this regime, Si on Si(OO1) exhibits anisotropic islands, as shown in Fig. 44. Ordering for such a system containing two coexisting phases (islands and 2D vapor) involves nucleation, growth, and coarsening, and is ultimately controlled by differences in boundary free energies between islands of various sizes and shapes. An immediate possibility to explain the observed anisotropic island shapes is to assume an anisotropic diffusion coefficient. This is likely because the substrate surface, consisting of dimer rows, is itself anisotropic. Another possibility is an anisotropic bond energy to the island boundaries. Modeling anisotropic diffusion coefficients, however, led to a negative prediction for island shape anisotropy; this is consistent with the additional observation that annealing made all the islands more isotropic with an equilibrium shape anisotropy of 3. Modeling the accommodation coefficient at the side of a growing dimer chain to be considerably less (- 0.1) than at the chain end led to the observed island shape anisotropy. Further questions arise as to the diffusion coefficient of Si on Si(OO1) and the effect of steps on the growth process. Regarding the latter, it was observed that the

-

(b) Figure 44. (a) 230 8, x 230 8, topographic image of 0.005 ML Si deposited at 475 K on Si(001). (b) Island shapes become more rounded with less anisotropy 600 K for 120 s (Mo et al., after annealing at 1989).

-

-

atoms do not attach at steps to form a single-height step but immediately form double-height steps (Mo et al., 1990b). This effect implies that the diffusion coefficient across steps is rather high. The diffusion coeficient, D, was measured (Mo, 1991) by statistically analyzing the number density of islands during deposition within a model relating D to island formation. If D is large, there is a greater chance for the growth of exsting islands, while if D is small, there is a higher probability to nu-

50


cleate new islands. Using anisotropic bonding as before and a diffusion anisotropy of 1000 (Mo, 1991),the value of D was found to be 0.67 eV with a pre-factor of cm2/s. Heteroepitaxial growth was studied in STM measurements of Ge on Si(OO1) (Mo et al., 1990). Ge growth on Si(OO1) follows the Stranski- Krastanov process in which the deposited material wets the surface forming a strained layer [ 3 atomic layers for Ge/Si(OOl)];when the surface energy of the strained layer becomes sufficiently low, three-dimensional (3D) clusters begin to form. It was found that the kinetics of 3D cluster formation proceeds via small intermediate (105) Ge facets that form on the strained layer. These clusters promote the accommodation of arriving atoms better than direct nucleation of new 3D clusters.

occupied states and V, = + 1.9 V probe occupied states. It is immediately apparent that (1) the images are displaced from each other both along [OOT] and along [IT01and (2) the shapes of individual features for opposite polarities are different. The localization of electrons (occupied states) about the As atoms and the localization of an empty orbital about the Ga atoms explains the lateral difference in the images. The separation in energy between the surface states reflects changes in the surface structure caused by the surface electronic structure. The detailed electronic structure was used to analyze the clean surface lattice relaxation. It was confirmed that the GaAs rows are rotated by -28" driving the surface bond hybridization towards a (planar) sp2 configuration to lower the surface energy.

2.4.3 GaAs(ll0)

2.4.4 Photoinduced Processes

Understanding the surface properties of 111- V compound semiconductor surfaces and interfaces is important for new device applications. Since the surface and interface properties of such compounds as GaAs are typically rather different from Si, STM studies of these materials have led to novel results directly related to the nature of the surfaces of compound semiconductors. In Sect. 1, it was noted that voltagedependent imaging of GaAs(ll0) is the prototype system to demonstrate the ability of STM to directly relate geometric and electronic structure. Chemical identification using valence band structure is typically difficult, but surface chemical analysis is surprisingly straightforward since the anion and cation species can be differentiated by comparing images acquired with opposite polarities (Feenstra et al., 1987b). In Fig. 4, boxes locate identical regions for which images with V, = - 1.9 V probe un-

Semiconductor substrates are usually rather highly doped so as to provide suf€icient room temperature conductivity for STM imaging without inducing a voltage drop across the substrate. Inducing thermally-stimulated carriers by heating the sample has been demonstrated as one means to increase the number of carriers for tunneling (Binnig, 1985). Illuminating the sample to form a photoconductive top layer was demonstrated as an alternative method to permit imaging of samples of low conductivity (van de Walle et al., 1987). In this study, an HeNe laser and a halogen lamp permitted imaging of a semi-insulating (e x 7 x lo' R cm) GaAs wafer and was presented as a means to image other insulators with STM. Optical illumination in combination with STM has also been used to study excited carrier relaxation on the nanoscale (Hamers and Cahill, 1990; Hamers and

-

-


Markert, 1990). Under DC illumination, it is possible to measure a voltage created across the space-charge region by optically-created electron - hole pairs which form a non-equilibrium charge distribution. In one study on an Si(l11)-(7 x 7) surface, this local surface photovoltage (SPV) was measured as a function of illumination intensity and position with the STM operating in a potentiometry mode (Hamers and Markert, 1990). The images showed that defects decrease the SPV in a region 25 8, in diameter. In these regions, the model developed suggested a recombination rate approximately four times higher in the defect region than in the ordered (7 x 7) surface. A time-resolved study of carrier lifetimes on an Si(lll)-(7x 7) surface was performed using a picosecond laser pump and the STM as a synchronous probe operated in a scanning capacitance arrangement (Hamers and Cahill, 1990). The time dependence of the SPV, as shown in Fig.45 was fit in terms of a simple model, where the SPV decay is T = Z D . exp { - e [ S P V ( t ) ] / ( k T ) } ,the value of T D deduced from the data was -1 ps.

-

. _.-....

50 ns

0 10 20 30 40 50 Pulse separation (units of 13.1 ns)

Figure 45. Time-dependence of surface photovoltage as a function of delay time between optical pulses (Hamers and Cahill, 1990).

51

2.5 Metal- Semiconductor Interfaces Several aspects of advanced microelectronics device technology require an understanding of the structure and electronic properties of metal-semiconductor contacts in atomistic detail. This assertion is justified by the demonstration that the Schottky-barrier heights are intimately related to the structural details at abrupt epitaxial interfaces (Tung, 1984; Heslinga et al., 1990); these observations differ markedly from the classical theory of Schottky-barrier formation (Schottky, 1938; Schottky, 1940). Ulimately controlling metal film growth requires the control of chemistry, i.e. avoiding undesirable compound formation, and growth kinetics, to achieve epitaxial structures. Development of the macroscopic metal semiconductor interface, with its corresponding electronic properties, begins with sub-monolayer coverages of metal atoms, passes through the process of metallization, and continues to the development of a multilayer film, which may exhibit a rectifying or an ohmic behavior. Metal films typically do not grow epitaxially layer-bylayer (Frank-van der Merwe) on semiconductor surfaces due to the surface kinetics at the substrate temperatures at which deposition is typically performed. Two alternate growth modes are Stranski-Krastanov, involving the initial formation of a monolayer followed by 3D island (cluster) growth, or Volmer- Weber, involving only 3D island growth. STM can be used to measure the morphology of the surface in multilayer regime and island sizes and their distributions directly under various processing conditions. Metallic islands formed on a semiconducting surface are expected to undergo an insulator -+ metal transition at some critical three-dimensional size, and the transition can be char~

52


acterized by STS. To assess metallic behavior by detection of electronic states at E,, i.e. under zero-bias conditions, the spectroscopic dynamic range can be enhanced by taking current images at several sampletip separations (Feenstra, 1989) or by advancing the probe tip towards the sample during a voltage sweep (Feenstra and Mirtensson, 1988). One fundamental aspect of this problem, with roots in surface science, involves the evolution of the metal-semiconductor interface in its initial stages. Thin film science takes over in the sub-monolayer to fewlayer regime, where imaging provides input into growth processes, and spectroscopy can elucidate the chemical bonding interactions as well as the evolution of electronic properties. Finally, when the macroscopic thin film is complete, the relation between the electronic properties of the initial interface and that of the final metalsemiconductor junction may depend strongly on the unique properties of the buried interface. Cases in which STM has been employed to study metal-semiconductor interfaces in these regimes are discussed below. 2.5.1 Alkali-Metal- Semiconductor Interfaces Alkali-metal - semiconductor interfaces have been studied extensively as model metal-semiconductor systems, because the electronic structure of an alkali-metal atom is simple, chemical reactivity with the substrate is typically small, and a variety of ordered structures may exist in the first monolayer of growth. For example, STM studies indicated that Cs grows in one-dimensional chain structures on 111-V(110) surfaces for very low coverages (< 0.2 ML). This suggests the fascinating possibility of atom-thick lines, or “atomic wires”. STS,

however, found these structures to be insulating, but close-packed structures at higher coverages appeared to approach metallic behavior. In order to understand these observations, the dimensionality of the structure and the local density must be considered. Figure46A shows that the 1D structures at 0.2 ML consist of well-separated atomic Cs rows arranged in zigzag structures on GaAs(ll0) (Whitman et al., 1991a, c); similar structures were observed on InSb(ll0) (Whitman et al., 1991c). The classical picture of electron transfer between alkali-metal atoms and the substrate would predict ionic bonding and repulsive adsorbate-adsorbate interactions. However, this scenario is unlikely because the STM image indicates that anisotropic attractive interactions between Cs atoms induce the formation of Cs rows at the lowest coverages. As the coverage increases, triple chains that form local c (2 x 2) structures, and the room temperature saturated monolayer results in the formation of local c (4 x 4) structures. Although poor longrange order causes diffraction measurements to be insensitive to local structure, STM revealed that the c(4 x 4) structures are 5-atom Cs crystallites that correspond to the surface structure of Cs(ll0). Electron counting dictates that these structures should be metallic in a single-particle picture. In fact, at room-temperature saturation coverage, the packing density approaches that of metallic Cs. As shown in Fig. 46 B, the zero-bias conductivity indicates that the lower coverage structures are actually non-metallic, although the gap has narrowed. These results are consistent with recent studies of the spatially-averaged electronic excitation spectra under similar conditions, which show that the Cs/GaAs(llO) interface is non-metallic due to many-body effects in the ultrathin

-


53

structures would be non-metallic at zero temperature (DiNardo et al., 1990; Weitering et al., 1993a).

2.5.2 Growth of Trivalent Metals on Si(OO1)

(B) zoo

I

I

1

! I ’

150

h

100

(c) 2-D CS

d

v

g

4

50

5

U

0

(b) 1-D CE

a) GaAs

-50

I

-100

-2.0

-1.5

I

-1.0

4

I

1

-0.5

0.0

0.5

1.0

Voltage (V) Figure46. (A) STM image of one-dimensional Cs structure and of the c (2 x 2) structure at higher Cs coverage on GaAs(l10). (B) STS spectra for these regimes (Whitman et al., 1991 a).

overlayer. Further spectroscopic measurements on this system at room temperature indicated metallization when (three-dimensional) bilayers formed at higher coverages. On the basis of electron energy loss measurements there is some disagreement as to whether a gap still exists so that these

LEED and RHEED (reflective high-energy electron diffraction) studies have found that Al, Ga, and In form similar coverage-dependent series of ordered structures on the Si(001)2xl surface (Knall et al., 1986; Bourgiugnon et al., 1988a, b; Ide et al., 1989). Subsequent STM studies have provided details of these structures in the sub-monolayer regime (Baski et al., 1990; Baski et al., 1991; Nogami et al., 1991). Taking Al/Si(001) as an example, around room temperature an epitaxial 2 x 2 structure forms at 0.5 ML; this is preceded by the growth of one-dimensional A1 structures (Ide et al., 1989).The local structure comprising these overlayers represents A1 ad-dimers which form in a direction orthogonal to the clean Si(OO1)-2 x 1 surface dimers (Nogami et al., 1991).Occupied state STM images shown in Fig. 47 illustrate the evolution of these ad-dimer chains from 0.1 ML to 0.5 ML. Bias-dependent images at 0.4 ML are also shown in Fig. 47. Unfortunately, since individual A1 atoms could not be identified, due in large part to the complexity of the valence structure, the sites of A1 on the Si surface were not unambiguously resolved. Beyond 0.5 ML, the first layer is saturated and A1 clusters begin to form in a second layer in a Stranski-Krastanov growth mode. Recent calculations illustrate the mechanism for symmetric ad-dimer formation (Brocks et al., 1993) and account for the bias-dependent images observed. Single A1 atoms, which are not observed on the surface, are free to diffuse in any direction at room temperature with a small energy

54


Figure 47. (A) STM images showing the evolution of the AI/Si(001) interface at submonolayer coverages: (a) 0.1 ML, (b) 0.2 ML, (c) 0.3 ML, (d) 0.4 ML. (B) Images of 0.4 ML Al-covered surface acquired with (a) r/; = -2 V and (b) r/; = + 2 V (Nogami et al., 1991).

minimum at the symmetric hollow site between two pairs of Si dimers. Adding a second A1 atom on the surface results in the formation of a parallel ad-dimer between the substrate surface dimers without disruption, as shown in Fig. 47 and in agreement with previous calculations (Northrup et al., 1991). This configuration is preferred over ad-dimer configurations, either between the Si dimers and rotated by 90°, or forced to reside in the Si dimer rows, because favorable bond angles with minimal strain are possible. This provides a natural mechanism for the formation of the observed dimer chains oriented perpendicular to the clean surface dimer rows. A third adatom preferentially binds at a reactive site located next to the existing A1

dimer and situated energetically near E,. A fourth A1 atom achieves a minimum energy configuration by forming a second dimer. This process may be viewed as a surface polymerization reaction (Brocks et al., 1993). Electronically, the ad-dimer interacts with the n and n* states of the clean Si(OO1) dimers. The occupied local density of states near E , is localized near the Si atoms that have reacted with Al, as shown in Fig. 47. This represents remnants of the disrupted, but not broken, n bond of the clean surface. In the empty state image, the unoccupied dangling bond states of A1 are expected to appear between the Si dimers. This model is in qualitative agreement with experimental observations (Nogami et al., 1991).It is also expected that, as the coverage is increased, repulsive interactions will create dimer rows with p ( 2 x n) periodicity. 2.5.3 Ambiguities in Structural Determinations

The exclusive use of STM as an imaging or even as a spectroscopic probe in order to obtain direct structural information must be done with care, especially in metal-semiconductor systems. There are examples in the literature where controversy has developed around the interpretation of STM images to obtain structural models for metal-semiconductor systems. Since the valence structure which is probed is likely to change dramatically as the metal-semiconductor interface develops good insight into the evolution of local electronic structure from theoretical calculations as well as element-specific probes [e.g., Auger, X-ray photoelectron spectroscopy (XPS), Rutherford backscattering (RBS)] to provide absolute and relative coverages, and structural probes extending beneath the top layer, are crucial to couple with STM data. Recently, sophisticated


theoretical calculations have made great progress in testing various structural models to provide simulated STM images. We briefly consider the Ag/Si(l11)J? x ,,h and the Na/Si(lll)-3 x 1 systems as examples where complementary techniques and high-quality theory have been required to provide a fully consistent interpretation of the STM images to arrive at the structure. Si(lli)-fix

& Ag

Obtaining the structure of the Si(l11),,hx 4$ Ag interface has been particularly difficult over the years because of seemingly conflicting results from an array of surface science techniques. A few of the structures that have been proposed are shown in Table 1. Here a knowledge of the absolute Ag coverage can be used to distinguish between structural models. STM studies of the initial stages of Ag nucleation on the Si(l11)7x 7 surface at < 130 "C shows that Ag atoms bond to the dangling bonds of the second atomic layer in the 7 x 7 unit cell with the subsequent formation of two-dimensional islands of close-packed Ag atoms while the 7 x 7 unit cell is preserved (Tosch and Neddermeyer, 1988). A 3 x 1 structure can be formed by exposure to an Ag flux above 500°C (Wilson and Chiang, 1987b) (see below). The Si(l1l)-,,h x $ Ag structure forms after deposition of 1 ML Ag at 460°C (van Loenen et al., 1987), or for room N

-

N

Table 1. Selected proposed Si(1 l l ) - J j x J 3 Ag structures and Ag coverages. Structure Embedded trimer (ET) Honeycomb (H) Honeycomb-chain-trimer (HCT)

55

temperature (RT) deposition followed by annealing at 200 - 500 "C (Wilson and Chiang, 1987 b). Occupied- and unoccupied-state images of the Si(l1I)-$ x $ Ag structure are shown in Fig.48 (Wan et al., 1992b). An early STM study of structure (van Loenen et al., 1987)decided on the ET model based on CITS spectra, the non-metallic nature of the surface, and prior ion scattering results. This picture requires that the imaged atoms are Si atoms atop the embedded Ag atoms. Another set of studies decided upon the H model, assuming that Ag atoms form the image (Wilson and Chiang, 1987b), and by further considering the registration of the structure with respect to the 7 x 7 nucleated at lower Ag coverages (Wilson and Chiang, 1987a). Two theoretical calculations, however, found that the HCT model produces a consistent explanation for the majority of surface science studies, including further bias-dependent STM studies. In the latter, the registration arguments previously put forth were shown not to be unique depending on the presence or absence of a step at the domain boundary. While this structure finally appears to be resolved on the basis of comparisons of STM (Wan et al., 1992b) and other techniques, it is clear that calculations of total energy values for several structures (Ding et al., 1991), along with comparisons of the calculated electronic structure (Ding et al., 1991; Watanabe et al., 1991) with bias-dependent imaging, are essential in order to perform a dependable structural analysis on the basis of the spatial-dependence of the valence electronic structure.

fi

Ag coverage

1 ML 213 M L 213 ML

3x1

The Si(ll1) surface exhibits an adsorbate-induced 3 x 1 reconstruction when it

56


atom and without complementary techniques, the Na-, Li-, or Ag-induced 3 x 1 @ @ have been interpreted in terms of an or.Om6!@ @Omdered reconstruction with an overlayer .O,O,J @O,O, coverage of 2/3. It is agreed that a channel @Om 100 A. Figure 130a shows an image of grooves spaced 2 pm apart on a Si wafer. It is important to note that the van der Waals interaction is materialdependent, so that contrast in constant

-

-

134


ris et al., 1989; Terris et al., 1990),as well as ferroelectric domains (Saurenbach and Terris, 1990) at surfaces, can be obtained by imaging forces due to electrostatic or polarization charge, respectively. Charge force microscopy has demonstrated that the distribution of surface charge, deposited by inducing discharges between a grounded tip and sample (PMMA, sapphire, etc.), can be imaged with a lateral resolution of I 0.2 pm with a vibrating tip situated 10-100 nm from the surface. The interaction force of interest comes from the interaction of the surface charge with an image charge induced in the tip. The tip also responds to the (uniform) charge distribution at the back of the sample due to varying its potential as well as to the van der Waals force. The van der Waals force attenuates as a function of sampletip separation significantly faster than the electrostatic force, and can be neglected. A series of corlstant force gradient images take over a period of 1 hour is presented in Fig. 131A. At different sample biases, the image profiles of the surface charge change, as shown in Fig. 131 B, proving that the nature of the interaction is electrostatic and not due to surface topography. The sign of the charge can be obtained by taking such a series of images (Fig. 131B), or by direct modulation of the sample bias (Terris et al., 1989). In Fig. 131A, the charge is seen to decay and becomes spatially-broadened ; charge redistribution over the surface is significantly more rapid than would be observed by a macroscopic measurement, indicating the unique information that spatial resolution provides. Furthermore, during contact electrification of polycarbonate and PMMA it was found that both signs of charge could be deposited simultaneously, as shown for polycarbonate in Fig. 132 (Terris et al., 1989).This novel observation has not been completely exN

Figure 130. (a) Constant force gradient profile of a grooved silicon wafer; (b) constant force gradient profile of a flat Si wafer partially coated with photoresist (Martin et al., 1987).

force gradient images comes not only from surface topography but also if the tip begins to interact with another component on the surface. This is demonstrated in an image, of the junction between Si and photoresist, as shown in Figure 130b.

3.4.2 Electrostatic Forces The measurement of the spatial distribution of charges on surfaces of insulating materials can be obtained by AFM (Terris et al., 1990). In this way, the microscopic spatial details of contact electrification, or triboelectrification (Stern et al., 1988; Ter-

135

3 Atomic Force Microscopy

t

0 min

24 prn-

t = 6 0 min

(B)

i bl

A

U I[

.U.

.I). :&

U

technique has been estimated to be about three electronic charges, i.e., 3e (Terris et al., 1989).

.I).

3.4.3 Magnetic Forces

VB = -6V

VB = +6V

..... V 20 pm

t -

f

-

Figure 131. (A) Series of constant force gradient contours over a region of deposited charge shown in inset showing charge dissipation (Stern et al., 1988): (B) Constant force gradient contours for different bias voltages with charge distribution schemes (Terris et al., 1990).

plained and may be due to the method of charge transfer; however, the result suggest that charge measured by a macroscopic measurement may involve a balance between a bipolar distribution. The extreme sensitivity of this resonantly-enhanced

Magnetic microstructure is an important materials issue with applications extending from basic understanding of the interaction of microscopic magnetic domains to improving materials for high density information storage. The interaction of magnetized tips, either permanently or inductively magnetized, with a surface of a magnetic material can be imaged with the AFM operated in the non-contact detection mode. Both hard and soft magnetic materials can be imaged. In the initial experiments to demonstrate the feasibility of the magnetic force microscope, images of thin film recording heads were obtained using two modes running either AC or DC currents through the head to measure dynamic and static fields, respectively. With the magnetization modulated and with the tip set 10 nm from the sample, pole pieces could be imaged with 100 nm lateral resolution. To measure static fields, images with DC currents run in both directions were obtained

-

-

136


Figure 132. Images of five deposited charge regions on a polycarbonate surface (+, white; -, black) (Terris et al., 1989).

(Fig. 133a, b). While a net attractive interaction resulted due to tip-induced magnetization, for one current direction the left pole produced the main attractive force while for the other direction, the right pole dominated. A difference image (Fig. 133 c) shows a magnetic field pattern that defines the pole pieces. Magnetic force images of single-crystal iron whiskers (Goddenhenrich et al., 1990b) and permalloy thin films (Mamin et a1-7 1989) were obtained to demonstrate the ability of the technique to distinguish the structure of domain walls. In a constant force gradient image of the 2.5 pm permalloy thin film shown in Fig. 134, Bloch walls appear as bright or dark lines and the domain structure is comparable to that by Kerr imaging techniques. The shift from bright to dark at the arrow indicates the position of a possible Bloch line. These images were obtained with a bias on the sample to ensure a net attractive force and a magnetic tip at a distance of 150 nm from the surface. When the tip was brought close to the surface of a 30nm permalloy thin film, images became distorted, sug-

-

-

(c)

0 2 4 6 micron

Figure 133. Magnetic force images of a thin-film recording head with a current of (a) +10mA, (b) - 10 mA; (c) difference between (a) and (b) (Martin and Wickramasinghe, 1987).

Figure 134. Magnetic field image of domain walls on permalloy thin film. The bright/dark lines signify Bloch walls and the arrow defines a possible Bloch line (Mamin et al., 1989).

4 Manipulation of Atoms and Atom Clusters on the Nanoscale

gesting wall motion due to a reversible tipinduced magnetic structure in the sample when the sample coercivity is locally exceeded.

4 Manipulation of Atoms and Atom Clusters on the Nanoscale A most challenging current goal of materials science is to manipulate atoms at the atomic level in order to fabricate high-density structures for technological applications ranging from microelectronics to bioengineering. The limit in the miniaturization of high density information storage devices or lithography is the development of the technology to produce and utilize structures of atomic dimensions. At this level, the STM and AFM can be viewed as read/write devices - that is, information can be read by scanning the surface with atomic resolution, manipulated by moving atoms or changing the states of atoms on the magnetic with the tip, and re-read by scanning over the modified surface. It is well-known that some types of surface modification can occur by uncontrolled tip crashes during STM operation. Controlled writing of grooves in gold through mechanical deformation was first demonstrated by Abraham et al. (1986). Control of atomic-scale surface modification derives from the exploitation of the mechanisms involved in the tip-atom interaction and demands on ability to index the tip so as to successfully return to the same point on the surface repeatedly. In this context, a nanoscale memory element could be envisioned as the deposition, removal, or transfer of an adsorbate atom at a specific surface site or region using the STM tip (Quate, 1991). The information contained in this and other atomic-sized “data bits” could then be read with the

137

same tip in the scanning mode. The prospect of actually realizing this vision has been demonstrated in recent STM studies, in which the xenon atoms were moved into desired locations and an “atom-matrix’’ pattern was subsequently imaged in ultrahigh vacuum at liquid helium temperature (Eigler and Schweizer, 1990). It this useful to show that direct and indirect lithography ot atomic-sized structures can be achieved on electronic materials. In this regard, it has been shown that silicon atoms and atom clusters can be transferred between one location and another on the substrate using the STM tip as a carrier (Lyo and Avouris, 1991). This was achieved by pulsing the voltage on the STM tip to pickup and subsequently deposit the atoms. Besides bi-directional transfer of material between the surface and the tip (Lyo and Avouris, 1991), the attraction of chemisorbed atoms along a surface by the tip and tip-induced surface chemical modification has also been demonstrated. Extensions of these techniques to customform or manipulate species at the molecular level are the basis for site-specific chemistry and biochemistry. The magnitude of forces involved for moving atoms along the surface over potential corrugations should be quite different from those involved in transferring atoms between the tip and the sample, or vice-versa (Eigler and Schweizer, 1990). Thus, the mechanisms involved for atom or cluster manipulation at surfaces and specific application of such structures require new physical ideas regarding magnitudes and distance-dependences of highly localized forces. Besides this work, surface modification by direct contact of tip and sample using a force microscope may be viewed as another new area for exploration and exploitation (Weisenhorn et al., 1990). Developing such capabilities opens up

138


many possibilities for future applications in advanced materials technology.

4.1 Transfer of Atoms and Atom Clusters Between Tip and Sample The first example of atomic-scale surface modification was reported by Becker et al. for the creation of structures such as the Ge(l11) surface (Becker et al., 1990). The surface was modified by holding the tip over a surface site, raising the tip-sample bias to - 4.0 V (20 pA current), and rapidly withdrawing the tip by -1 A. Following this procedure, images of the surface displayed isolated protrusions about 8 wide and 1 A high, as seen in Fig. 135. Since the process occurred with a higher success rate when the tip had previously contacted the surface, it was proposed that the Ge atoms, acquired from previous tip -surface contact, were being deposited from the tip onto the surface. Positioning an STM tip in close proximity to the surface lowers the potential barrier to field-evaporation and this effect can indeed serve as a means to transfer atoms or clusters of atoms between the tip and the sample. The condition to confirm transfer via a field evaporation mechanism is the existence of a threshold bias voltage for deposition or removal of matter. Subsequent to the work of Becker et al. (1990), N

1.6

1

-

10

20

30

40

--

-

-

-

L 0

the existence of such a threshold for deposition at a selected site by pulsing the tipsample bias was demonstrated (Mamin et al., 1990; Lyo and Avouris, 1991). Mamin et al. (1990) utilized a field evaporation process to deposit 10 nm diameter gold dots of height 2.5 nm onto a gold surface using a gold tip as the source, as shown in Fig. 136. Such dimensions are significantly smaller than the 100nm Ga lines which had previously been drawn by ion emission from a liquid metal ion source (Bell et al., 1988). The experiments of Mamin et al. have demonstrated the existence of a pulse height threshold below which the probability of deposition was nearly zero and above which the probability increased to nearly one. Examination of the dependence of the threshold voltage on the tip-sample distance confirmed a constant gap impedance indicating the need for a critical field of 0.4V/A. Considering a model in which deposition occurs via ionization followed by field evaporation for an isolated tip, fields of 2-7 V/A were predicted, and, for gold, values of 3.5 V/ have been measured. The critical field is lowered with the two electrodes in close proximity so that the atomic potentials begin to overlap and the effective barrier height for evaporation is lowered. Even under these conditions, estimates of 1-3 V/A are still higher than the observed threshold

5 0 0 Distance ( A )

t

I

I

I

J

I0

20

X)

40

50

Figure 135. Scans of surface height (left) before and (right) after impression (Becker et al., 1987).


139

field-evaporation from the surface to the tip by a + 3 V pulse after the tip was placed 3 8, from the surface. It was found that smaller amounts of Si were removed when the tip was closer to the surface and the amplitude of the voltage pulse was made smaller. For example, Fig. 137 shows the removal and re-deposition of a single Si atom; here the tip-sample distance was 5 8, and the pulse was + 1 V. Based on current versus tip displacement curves, it was proposed that the Si most likely resides at the apex of the tip during transfer. In assessing the mechanisms for the transfer of material, especially at very small distances, consideration must also be given to the modification of the semiconductor covalent bonds by large local current densities, to chemical interactions between the Si atom(s) and the tungsten tip, and to mechanical effects. It should be noted that, while mechanical contact does disturb the surface, it cannot be used as the pulsedfield process for controlled material transfer.

-

-

Figure 136. (a) Mohnds of gold made by applying voltage pulses between a gold tip and the sample. (b) Array of mounds formed on a stepped gold surface (Mamin et al., 1990).

4.2 Tip-Induced Lateral Motion of Atoms on Surfaces fields. While quantitative disagreements still exist, the presence of a bias threshold provides evidence that a field evaporation mechanism drives the transfer of material. Not only can field evaporation occur from the tip to the sample. Transfer of material sample-to-tip through a field evaporation process should also be possible, and this effect has recently been demonstrated. In particular, the manipulation of Si atoms and Si clusters on an Si(ll1) surface has been demonstrated by Lyo and Avouris (Lyo and Avouris, 1991), whereby material was transferred in a controlled fashion from the substrate onto the tip for re-deposition at another place on the surface. Removal of Si atoms or clusters involved

The potential barrier to lateral movement of atoms is generally lower than the barrier for vertical motion, or removal. In order to use the STM tip to move an atom

~~

-

-

--

--

-

Figure 137. Removal and re-deposition of a single Si atom on an Si(ll1) surface, Left: before voltage pulse. Middle: after voltage pulse. Right: after re-deposition (Lyo and Avouris, 1991).

140


across a surface, two types of tip-atom interactions may be envisioned - van der Waals or electrostatic forces. Recently, Eigler and Schweizer demonstrated the precise position of xenon atoms on an Ni(l10) surface and conducted preliminary tests regarding the lateral attractive interaction between the tip and the atom, as shown in Fig. 138 (Eigler and Schweizer, 1990). Xenon bonds to the surface by physisorption so the experiments must be performed at low temperatures. In the experiments of Eigler and Schweizer, the STM and the vacuum chamber in which it was housed were cooled directly with liquid helium. The advantage of this arrangement is that

Figure 138. Sequence of STM images acquired during the construction of a patterned array of xenon atoms on an Ni(ll0) surface (Eigler and Schweizer, 1990).

the system in thermal equilibrium is very stable and cryopumping by all the cold surfaces creates such a high vacuum that the sample surface can remain clean for weeks. The process of atomic positioning of Xe by lateral tip-atom interactions involved the following steps: (1) the Ni surface was exposed to Xe, (2) the tip was placed directly over a physisorbed Xe atom and lowered to increase the attractive force by increasing the tunneling current, (3) the tip/atom combination was moved to the desired site, (4) the tip was withdrawn by reducing the tunneling current and subsequent imaging was performed to establish the success of the operation. It has already been noted that the ability to image a closed-shell atom such as Xe at such small biases only exists because the Xe 6s resonance occurs near the Fermi level of the substrate (Eigler et al., 1991b). In these experiments, both imaging and motion could be performed at a tip bias of 10 mV, while higher biases increased the interaction distance. The ability to displace Xe atoms was found to be polarity-independent, indicating that the van der Waals attractive interaction was the operative mechanism for atomic manipulation. It was also found that the close-packing distance between Xe atoms was fixed, being a property of the closed-shell atom, so artificial structures of higher density could not be obtained. Studying physisorbed atoms at low temperatures has provided a good deal of fundamental information on mechanisms for atomic manipulation. However, operating at these temperatures is experimentally restrictive. Atomic manipulation of chemisorbed systems at room temperature is a desirable extension of this work. Due to the stronger interactions of chemisorbed atoms with the surface, local manipulation may_ permit the formation of artificial or_ dered structures more readily since the


atoms need not reach thermal equilibrium, e.g. by annealing, as is usually the case. Whitman et al. (1991c) demonstrated that, by pulsing an STM tip set above submonolayer coverages of Cs atoms adsorbed on a GaAs(ll0) surface, the Cs atoms can be rearranged laterally through field-induced diffusion. The Cs/GaAs(llO) system is particularly interesting since it has been discovered that, at such low coverages, Cs forms various one-dimensional structures along the [110] direction (First et al., 1989a) and other two-dimensional structures at higher coverages (Whitman et al., 1991a). The fact that one-dimension equilibrium structures form is consistent with the anisotropic GaAs(ll0) surface structure. With a distribution of Cs atoms on the surface, moderate pulsing of the tip bias was found to attracts Cs atoms towards the tip anisotropically so that new chains formed in the local region of the tip, as shown in Fig. 139. Larger pulses aggregated Cs into mounds around the tip. Other pulsing conditions produced ordered structures not seen on the Cs/ GaAs(l10) interface in thermal-equilibrium. The fact that pulse width and pulse amplitude result in larger effects in the tip region implies a field-induced diffusion process. The spatially-varying field produced by the tip produces a potential gra-

Figure 139. STM images of Cs on a GaAs(l10) surface (A) before and (B) after pulsing the sample bias with the tip in the center of the imaged area (Whitman et al., 1991c).

141

dient, or a force, laterally and vertically with the attractive interaction towards the tip. Estimates predict that the polarizability of a Cs atom on the semiconducting surface is considerably larger than on a metal surface. However, considering the smaller surface potential corrugations on metal surfaces, field-induced diffusion might also be applicable for these systems.

4.3 Nanoscale Modification by Tip-Induced Local Electron-Stimulated Desorption Nanoscale modification of the chemically-passivated Si(111):H -1 x 1 surface in vacuo (Becker et al., 1990) and in air (Dagata et al., 1990) has been demonstrated recently. It was previously established that the Si(ll1) surface can be made entirely unreactive by saturating dangling bonds with a layer of atomic hydrogen deposited by an ex situ, in-solution chemical process (Higashi et al., 1990). Arsenic-passivation of Si(111) and Ge(11l), performed in vacuo, had been demonstrated even earlier (Bringans et al., 1985; Olmstead et al., 1986). The H-passivated surface is one of the most ideal flat surfaces ever observed (Higashi et al., 1990). Becker et al. (Becker et al., 1990) have convincingly shown that using the STM in a field emission mode converts a localized area under the tip to a clean Si(l11)-2 x 1 surface by the electronstimulated desorption of H. STS measurements of the passivated surface regions showed no surface states, and spectroscopy of the 2 x 1 regions produced the previously-established Si(ll1)-2 x 1 surface state spectra (Stroscio et al., 1986). This result is significant in two regards. First, it shows that a low activation-barrier exists between the 1 x 1:H surface and the 2 x 1 n-bonded chain structure. Second, the Iocalized field-emission-induced desorption

142


process exhibits an energy dependence suggesting that H-desorption proceeds via excitation to the unoccupied o* level (- 8 eV kinetic energy) with an efficiency of 3 x lo-*. The spatial resolution depends on the geometry of the set-up, i.e. on the area of incidence of the field-emitted electrons. With the tip lo00 8, above the surface and a bias of 60 eV, the 2 x 1 region was found to be 8000 8, wide. If the tip was 40 8, away and had a lower bias, widths of 40 8, were obtained. For such a system, subsequent decoration of the clean areas and possible selective etching might be envisioned to produce permanent nanoscale patterns. Modification of the H-passivated Si(ll1) surface in air has also been reported (Dagata et al., 1990). The observed nanostructures appeared as 1-20 nm deep depressions with widths of the order of 100200 nm. These are areas where oxidation has taken place, so oxygen occupies the de-passivated regions of the substrate. The tip-induced process was considered to proceed by field-induced ionization of oxygen, resulting in diffusion-enhanced oxidation. In light of the results of Becker et al. (Becker et al., 1990),field-emission induced removal of H should also be considered.

-

--

N

-

-

4.4 Nanoscale Chemical Modification Various attempts at STM-assisted deposition or modification of chemical species at surfaces include etching lines on GaAs in an electrochemical cell (Lin et al., 1987), pinning large organic molecules to graphite surfaces by pulsing the tip bias (Foster et al., 1988),decomposing an organometallic (dimethyl cadmium) under an STM tip to write metal lines (Silver et al., 1987),and exposing polymethylmethacrylate resist using the localized tunneling current (McCord and Pease, 1987). In each of these

examples, the presence of the tip created a reaction of the chemical species to obtain desired surface features.

4.5 High-Temperature Nanofabrication Attempts at nanofabrication on Si surfaces maintained at high temperatures have recently demonstrated that the electrostatic tip-surface interaction coupled with the high diffusivity can permit atomic control, so that writing speeds of 10 nm/s can be obtained (Iwatsuki et al., 1992). High temperature imaging of Si surfaces has indicated that diffusion of the adatoms is high enough to form a 1 x 1 structure. For nanofabrication under similar conditions, the tip bias is raised and a constant tip-sample distance is maintained as the tip is scanned. The electric field strength is determined, not only by distance, but by bias, tip geometry, and tunneling current. Patterns with linewidths of 1-2 nm and depths of 0.3 nm have been obtained. Besides atom manipulation, larger structures can be formed. For example, applying a +4 V bias on the tip, the tip-induced electric field causes atoms to migrate to the tip and hexagonal pyramidal structures and quadrangular pyramidal structures have been formed on Si( 111)and Si (100),respectively, with a sample temperature of approximately 6OO0C, as illustrated in Fig. 140. When the polarity was reversed, craters were formed. The edges of these features revealed higher index planes or step structures.

4.6 Nanoscale Surface Modification Using the AFM Manipulation of molecules on surfaces has also been demonstrated using the AFM. In particular, Weisenhorn et al. (Weisenhorn et al., 1990) used an AFM tip to write on zeolite surfaces by moving

143


Figure 140. (a) Hexagonal pyramidal structures formed on Si(11l), and (b) quadrangular pyramidal structures formed on Si(100) obtained by scanning the tip with a + 4 eV bias over a sample maintained at 600°C (Iwatsuki et al., 1992). 5

molecules when large contact forces were applied. In this work, a layer of tert-butyl ammonium cations was adsorbed on a clinoptilolite surface in order to assist this. These cations are bound to the surface via surface ion adsorption and form clusters after injection of the solution on a time scale that could be monitored by the AFM. Using a force > N at selected locations while scanning, an “X” was written into the layer. Subsequent imaging at < N indicated that the clusters we connected in the pattern and that the pattern remained stable.

change of state and conductivity measurement are performed with the tip fixed above the surface, so imaging the atom is not required to test the state of the switch. That the Xe atom has actually moved to the tip was inferred, however, from the absence of Xe in a subsequent image. The change in conductance is due to the different localized sites for the atom in its two possible positions, which also changes the

8-

4.7 Towards Nanoscale Devices While the experiments of Eigler and Schweizer (1990) attained wide notoriety, particularly, when an “atom-matrix’’ display of the IBM logo using Xe atoms was fabricated, the use of the Xe-Ni(ll0) systems as an “atomic switch” was also demonstrated (Eigler et al., 1991a). In this regard, individual Xe atoms were reversibly transferred between the tip and the sample using voltage pulses of opposite polarities (f0.8 V) at low temperatures. The state of the switch was subsequently queried by measuring the tunneling conductance, which changes if the Xe atom is bound to the tungsten tip or the nickel surface. This process is illustrated in Fig. 141. The

i

9-

2

7-

m I

26-

Y

) . ’

c

2 L

5-

3 43-

‘-

A

1

1-

OO

B1L L

lb

20

30

40

L L I 50 60 70 80

Time (s) Figure 141. Time dependence of current through the switch during operation of the atomic switch (Eigler et al., 1991a).

144


effective tunneling distance on which the current is exponentially-dependent. In contrast to the work discussed above, fieldevaporation was excluded as a possible atom transfer mechanism since the ion states exist far above the Fermi level and no threshold electric field was required for the transfer. Two other proposed mechanisms still remain to be tested - electromigration and impurity heating, both due to the tunneling current in the vicinity of the Xe atoms.

5 Spin-offs of STM Non-Contact Nanoscale Probes The STM and AFM techniques have been discussed in previous sections of this article. Their application to a wide variety of problems in science and technology have been realized over a relatively short period of time. The physics of the electron tunneling process provides the STM with capabilities for both topographic and spectroscopic imaging of surfaces on the atomic scale. In contact and non-contact modes, the AFM probes surface forces with extremely high spatial resolution and force sensitivity. STM and AFM can operate in vacuum as well a in air and liquids opening these surface techniques to a host of other problems not typically associated with surface science, notably the study of biomolecular systems. STM and AFM are based on imaging in the near-field, i.e. the probe is in close proximity to the sample. Several new techniques that borrow from the philosophy and technology of STM/AFM instrumentation, i.e. adopting the near-field imaging process, using piezoelectric actuators, and, in some cases, taking advantage of spectroscopic capabilities, have either been demonstrated or proposed. Extensions of

STM/AFM include probing the optical, thermal, electrical, or chemical properties of surfaces. In Table 2, various techniques STM, AFM, and spin-offs - and their attributes are listed. Details of the techniques and their applications are discussed in the remainder of this section.

5.1 Scanning Near-Field Optical Microscope (SNOM) The spatial resolution of standard optical microscopy, i.e. far-field optical microscopy, is diffraction-limited to lengths of the order of the wavelength 1(actually 1/2.3). Thus the resolution limit for imaging at optical wavelengths is 0.2 pm. In the familiar far-field regime, an image is reconstructed all at once by a focusing lens. Significantly, optical imaging with considerably higher spatial resolution has been demonstrated using nearyield techniques. Considering the STM as a near-field probe with the tip localized near the sampling region, sequential responses to the tunneling of electrons at discrete points over the scanned region are assembled to form the image. For a near-field technique, the source or the probe must be small; the spatial resolution is roughly limited by the aperture size or the probe-sample distance. Near-field optical microscopy operates on the same principle as a physician’s stethoscope where the detector is much smaller than an acoustic wavelength (Pohl et al., 1984).The optical analog is the scanning near-field optical microscope (SNOM) in which light is channeled down a metalcoated quartz tip with an -10nm aperture at its end, and the tip is scanned over the surface. In the first manifestation of this instrument (Pohl et al., 1984),the tip was sequentially moved and lowered into contact with the sample at each sampling point using piezoelectric drives. Using

-

5 Spin-offs of STM - Non-Contact Nanoscale Probes

145

Table 2. Near-field surface characterization probes, Instrument

Acronym

Measurement parameter

Lateral resolution

STM AFM

< 0.2 nm < 0.2 nm

Scanning tunneling microscope Atomic force microscope Tribological force microscope Attractive force microscope Charge force microscope Magnetic force microscope

CFM MFM

electron tunneling current surface force/force gradient lateral force van der Waals force electrostatic force magnetic force

Scanning near-field optical microscope Photon scanning tunneling microscope Scanning thermal profiler Scanning chemical potential microscope Optical absorption microscope Scanning ion conductance microscope

SNOM PSTM STP SCPM OAM SICM

near-field optical reflection near-field optical transmission surface temperature thermoelectric voltage effects of light absorption ion current

samples consisting of e-beam lithographed patterns on glass slides, the transmitted signal at each point is measured by a photomultiplier, and an image is constructed. The first experiments found that features < 25 nm could be observed, and the resolution limit of this technique was estimated to be 5 - 10 nm.

-

5.2 Photon Scanning Thnneling Microscope (PSTM) When a beam generated by, for example, an He - Ne laser experiences total internal reflection inside a material (for example, at the face of a prism), an evanescent field exists just outside the planar surface. On a microscopic scale, this evanescent field is modulated by the surface optical properties and structure. If an optical fiber with a very fine end is immersed in the field - at a distance from the surface of the order of the wavelength, 1 - internal reflection is locally frustrated in the vicinity of the tip. Light can couple (photon tunneling) to the optical fiber because modification of the internal reflection produces non-zero transmittance. The light then propagates through

< 0.2 nm

< 100nm < 200 nm

< 100 nm

Nanoscale characterization of surfaces and interfaces

Nanoscale Characterization of Surfaces and Interfaces

Imaging of surfaces and interfaces

Physics of Surfaces and Interfaces

Physics of Surfaces and Interfaces

Physics of Surfaces and Interfaces

Encyclopedia of Materials Characterization: Surfaces, Interfaces, Thin Films

Surfaces and Interfaces for Biomaterials

Polymers at Surfaces and Interfaces

Surfaces and Interfaces of Liquid Crystals

Dynamics of Crystal Surfaces and Interfaces

Surfaces and Interfaces of Liquid Crystals

Encyclopedia of Materials Characterization: Surfaces, Interfaces, Thin Films (Materials Characterization Series)

Surfaces, Interfaces And Colloids. Principles and Applications

Optics and Spectroscopy at Surfaces and Interfaces

Solid surfaces, interfaces and thin films

Solid Surfaces, Interfaces And Thin Films

Chemical Bonding at Surfaces and Interfaces

Statistical thermodynamics on surfaces and interfaces

Chemical bonding at surfaces and interfaces

Chemical Bonding at Surfaces and Interfaces

Characterization of corrosion products on steel surfaces

Characterization of Corrosion Products on Steel Surfaces

Atomic Scale Characterization and First-Principles Studies of SiN Interfaces

Conjugated Polymer Surfaces and Interfaces: Electronic and Chemical Structure of Interfaces for Polymer Light Emitting Devices

Solid Surfaces, Interfaces and Thin Films (Springer 2001)

Nanoscale Communication Networks (Nanoscale Science and Engineering)

Physics and Chemistry of Interfaces

Nanoscale science and technology

Nanoscale Materials

Nanoscale characterization of surfaces and interfaces